The best way to learn a new framework is to build something with it. This tutorial, by Scott Guthrie, walks through how to build a small, but complete, application using ASP.NET MVC, and introduces some of the core concepts behind it.
The application is called "NerdDinner". NerdDinner provides an easy way for people to find and organize dinners online.
Download a free PDF version of this tutorial if you want to read the tutorial offline.