ADO.NET uses a connection string to connect to a datasource. The default connection string is defined in the Web.config. The DAL will use this to connect to the database. The server that ado.net connects to can be anywhere so long as the correct ports are opened on firewalls etc.
If your dal is in a separate assembly then you can write a simple DAL web app that references the DAL.BLL and exposes the required methods and objects as web services - either use a RESTFUL approach, SOAP, WCF, simple ASHX - whatever you like best. Then in your original app develop a new DAL that instead of using ADO.NET, consumes the web services. Keep the DAL interface the same so you can switch the new DAL in place without changing any BL or UI code.
WCF Dataservices could be your answer - depending on how much refactoring you want to do - http://msdn.microsoft.com/en-us/data/bb931106