Are you brand new to WinFX and would like to just read a little about what it does and doesn't do?
Then take a look at these documents:
- The new user interface capabilities: Architectural Overview of the Windows Presentation Foundation
- Distributed communication: Introduction to Building Windows Communication Foundation Services
- Workflow enabling applications: Introducing Microsoft Windows Workflow Foundation: An Early Look
Your next port of call should then be the online SDK for WinFX http://winfx.msdn.microsoft.com/library/