Some time ago Jim Cheshire wrote a book on VWD 2008 and recently book publisher kindly allowed us to provide four chapters as free downloadable PDF files. The following chapters are available:
Creating Web sites
Creating and Managing CSS Styles
Applying CSS to Web Forms
Debugging ASP.NET Applications
You can find link to download at VWD section on ASP.NET Web site (look for Visual Web Developer Books section at the right side) or download ZIP file directly from here.