LINQ to SQL only supports 1 to 1 mapping of database tables, views, sprocs and functions available in Microsoft SQL Server. It’s a great API to use for quick data access construction to relatively well designed SQL Server databases. LINQ2SQL was first released with C# 3.0 and .Net Framework 3.5.
LINQ to Entities (ADO.Net Entity Framework) is an ORM (Object Relational Mapper) API which allows for a broad definition of object domain models and their relationships to many different ADO.Net data providers. As such, you can mix and match a number of different database vendors, application servers or protocols to design an aggregated mash-up of objects which are constructed from a variety of tables, sources, services, etc. ADO.Net Framework was released with the .Net Framework 3.5 SP1.
This is a good introductory article on MSDN:
Introducing LINQ to Relational Data