Tested on Windows Phone 8.0 and 8.0 SDK.
Just add a collection of brushes into the PieChart structure.
Using XAML
<chart:PieChart Height="300" Width="400" TitleMemberPath="Title" ValueMemberPath="Value">
<chart:PieChart.Brushes>
<SolidColorBrush Color="Red"/> <!-- color item #1 -->
<SolidColorBrush Color="Green"/> <!-- color item #2 -->
<SolidColorBrush Color="Blue"/> <!-- color item #3 -->
</chart:PieChart.Brushes>
<chart:PieChart.DataSource>
<local:PieDataCollection>
<local:PieData Title="Democrat" Value="123"/>
<local:PieData Title="Republic" Value="213"/>
<local:PieData Title="independent" Value="123"/>
</local:PieDataCollection>
</chart:PieChart.DataSource>
</chart:PieChart>
Using C#
public void LoadColors()
{
System.Windows.Media.SolidColorBrush red = new System.Windows.Media.SolidColorBrush();
red.Color = Color.FromArgb(0xFF, 0xFF, 0x00, 0x00);
System.Windows.Media.SolidColorBrush green = new System.Windows.Media.SolidColorBrush();
green.Color = Color.FromArgb(0xFF, 0x00, 0xFF, 0x00);
System.Windows.Media.SolidColorBrush blue = new System.Windows.Media.SolidColorBrush();
blue.Color = Color.FromArgb(0xFF, 0x00, 0x00, 0xFF);
this.PieChart.Brushes.Add(red); // add red
this.PieChart.Brushes.Add(green); // add green
this.PieChart.Brushes.Add(blue); // add blue
this.PieChart.DataSource = Data; // set the datasource
}