Here's the TabItemStyle from Blend.
The line you want is the mainBorder near the very beginning. You can see that the border brush that you choose is being applied but the border thickness isn't allowing it to really show. I changed it to 2,2,2,0 and I got a red border around the tabitem.

<Style x:Key="TabItemStyle1" TargetType="{x:Type TabItem}">
<Setter Property="FocusVisualStyle" Value="{StaticResource FocusVisual}"/>
<Setter Property="Foreground" Value="Black"/>
<Setter Property="Background" Value="{StaticResource TabItem.Static.Background}"/>
<Setter Property="BorderBrush" Value="{StaticResource TabItem.Static.Border}"/>
<Setter Property="Margin" Value="0"/>
<Setter Property="Padding" Value="6,2,6,2"/>
<Setter Property="HorizontalContentAlignment" Value="Stretch"/>
<Setter Property="VerticalContentAlignment" Value="Stretch"/>
<Setter Property="Template">
<Setter.Value>
<ControlTemplate TargetType="{x:Type TabItem}">
<Grid x:Name="templateRoot" SnapsToDevicePixels="true">
<Border x:Name="mainBorder" BorderBrush="{TemplateBinding BorderBrush}" BorderThickness="2,2,2,0" Background="{TemplateBinding Background}" Margin="0">
<Border x:Name="innerBorder" BorderBrush="{StaticResource TabItem.Selected.Border}" BorderThickness="1,1,1,0" Background="{StaticResource TabItem.Selected.Background}" Margin="-1" Opacity="0"/>
</Border>
<ContentPresenter x:Name="contentPresenter" ContentSource="Header" Focusable="False" HorizontalAlignment="{Binding HorizontalContentAlignment, RelativeSource={RelativeSource AncestorType={x:Type ItemsControl}}}" Margin="{TemplateBinding Padding}" RecognizesAccessKey="True" SnapsToDevicePixels="{TemplateBinding SnapsToDevicePixels}" VerticalAlignment="{Binding VerticalContentAlignment, RelativeSource={RelativeSource AncestorType={x:Type ItemsControl}}}"/>
</Grid>
<ControlTemplate.Triggers>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsMouseOver, RelativeSource={RelativeSource Self}}" Value="true"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Left"/>
</MultiDataTrigger.Conditions>
<Setter Property="Background" TargetName="mainBorder" Value="{StaticResource TabItem.MouseOver.Background}"/>
<Setter Property="BorderBrush" TargetName="mainBorder" Value="{StaticResource TabItem.MouseOver.Border}"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,1,0,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,1,0,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsMouseOver, RelativeSource={RelativeSource Self}}" Value="true"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Bottom"/>
</MultiDataTrigger.Conditions>
<Setter Property="Background" TargetName="mainBorder" Value="{StaticResource TabItem.MouseOver.Background}"/>
<Setter Property="BorderBrush" TargetName="mainBorder" Value="{StaticResource TabItem.MouseOver.Border}"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,0,1,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,0,1,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsMouseOver, RelativeSource={RelativeSource Self}}" Value="true"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Right"/>
</MultiDataTrigger.Conditions>
<Setter Property="Background" TargetName="mainBorder" Value="{StaticResource TabItem.MouseOver.Background}"/>
<Setter Property="BorderBrush" TargetName="mainBorder" Value="{StaticResource TabItem.MouseOver.Border}"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="0,1,1,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="0,1,1,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsMouseOver, RelativeSource={RelativeSource Self}}" Value="true"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Top"/>
</MultiDataTrigger.Conditions>
<Setter Property="Background" TargetName="mainBorder" Value="{StaticResource TabItem.MouseOver.Background}"/>
<Setter Property="BorderBrush" TargetName="mainBorder" Value="{StaticResource TabItem.MouseOver.Border}"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,1,1,0"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,1,1,0"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsEnabled, RelativeSource={RelativeSource Self}}" Value="false"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Left"/>
</MultiDataTrigger.Conditions>
<Setter Property="Opacity" TargetName="contentPresenter" Value="0.56"/>
<Setter Property="Background" TargetName="mainBorder" Value="{StaticResource TabItem.Disabled.Background}"/>
<Setter Property="BorderBrush" TargetName="mainBorder" Value="{StaticResource TabItem.Disabled.Border}"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,1,0,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,1,0,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsEnabled, RelativeSource={RelativeSource Self}}" Value="false"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Bottom"/>
</MultiDataTrigger.Conditions>
<Setter Property="Opacity" TargetName="contentPresenter" Value="0.56"/>
<Setter Property="Background" TargetName="mainBorder" Value="{StaticResource TabItem.Disabled.Background}"/>
<Setter Property="BorderBrush" TargetName="mainBorder" Value="{StaticResource TabItem.Disabled.Border}"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,0,1,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,0,1,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsEnabled, RelativeSource={RelativeSource Self}}" Value="false"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Right"/>
</MultiDataTrigger.Conditions>
<Setter Property="Opacity" TargetName="contentPresenter" Value="0.56"/>
<Setter Property="Background" TargetName="mainBorder" Value="{StaticResource TabItem.Disabled.Background}"/>
<Setter Property="BorderBrush" TargetName="mainBorder" Value="{StaticResource TabItem.Disabled.Border}"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="0,1,1,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="0,1,1,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsEnabled, RelativeSource={RelativeSource Self}}" Value="false"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Top"/>
</MultiDataTrigger.Conditions>
<Setter Property="Opacity" TargetName="contentPresenter" Value="0.56"/>
<Setter Property="Background" TargetName="mainBorder" Value="{StaticResource TabItem.Disabled.Background}"/>
<Setter Property="BorderBrush" TargetName="mainBorder" Value="{StaticResource TabItem.Disabled.Border}"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,1,1,0"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,1,1,0"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsSelected, RelativeSource={RelativeSource Self}}" Value="false"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Left"/>
</MultiDataTrigger.Conditions>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,1,0,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,1,0,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsSelected, RelativeSource={RelativeSource Self}}" Value="true"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Left"/>
</MultiDataTrigger.Conditions>
<Setter Property="Panel.ZIndex" Value="1"/>
<Setter Property="Margin" Value="-2,-2,0,-2"/>
<Setter Property="Opacity" TargetName="innerBorder" Value="1"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,1,0,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,1,0,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsSelected, RelativeSource={RelativeSource Self}}" Value="false"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Bottom"/>
</MultiDataTrigger.Conditions>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,0,1,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,0,1,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsSelected, RelativeSource={RelativeSource Self}}" Value="true"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Bottom"/>
</MultiDataTrigger.Conditions>
<Setter Property="Panel.ZIndex" Value="1"/>
<Setter Property="Margin" Value="-2,0,-2,-2"/>
<Setter Property="Opacity" TargetName="innerBorder" Value="1"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,0,1,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,0,1,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsSelected, RelativeSource={RelativeSource Self}}" Value="false"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Right"/>
</MultiDataTrigger.Conditions>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="0,1,1,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="0,1,1,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsSelected, RelativeSource={RelativeSource Self}}" Value="true"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Right"/>
</MultiDataTrigger.Conditions>
<Setter Property="Panel.ZIndex" Value="1"/>
<Setter Property="Margin" Value="0,-2,-2,-2"/>
<Setter Property="Opacity" TargetName="innerBorder" Value="1"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="0,1,1,1"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="0,1,1,1"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsSelected, RelativeSource={RelativeSource Self}}" Value="false"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Top"/>
</MultiDataTrigger.Conditions>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,1,1,0"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,1,1,0"/>
</MultiDataTrigger>
<MultiDataTrigger>
<MultiDataTrigger.Conditions>
<Condition Binding="{Binding IsSelected, RelativeSource={RelativeSource Self}}" Value="true"/>
<Condition Binding="{Binding TabStripPlacement, RelativeSource={RelativeSource AncestorType={x:Type TabControl}}}" Value="Top"/>
</MultiDataTrigger.Conditions>
<Setter Property="Panel.ZIndex" Value="1"/>
<Setter Property="Margin" Value="-2,-2,-2,0"/>
<Setter Property="Opacity" TargetName="innerBorder" Value="1"/>
<Setter Property="BorderThickness" TargetName="innerBorder" Value="1,1,1,0"/>
<Setter Property="BorderThickness" TargetName="mainBorder" Value="1,1,1,0"/>
</MultiDataTrigger>
</ControlTemplate.Triggers>
</ControlTemplate>
</Setter.Value>
</Setter>
</Style>