Here are couple free resources for learning Visual Studio 2010:
Product overview: http://download.microsoft.com/download/C/D/3/CD39BB69-35CC-458A-B4EB-2F928B58FB4B/VisualStudio2010_ProductOverview.pdfMoving to Visual Studio 2010 e-Books:http://www.microsoft.com/downloads/details.aspx?familyid=560A5365-5C62-488A-91ED-A779E0E33AC4&displaylang=enHow Do I? Videos for Visual Studio 2010http://msdn.microsoft.com/en-ca/vstudio/ff459609.aspxVisual Studio 2010 Resource Kithttp://www.microsoft.com/downloads/details.aspx?displaylang=en&FamilyID=5688c9ba-5071-4d9d-8794-c164f21a058cA Lap Around VSTS 2010 (an old one but very good)http://blogs.msdn.com/controlpanel/blogs/posteditor.aspx?SelectedNavItem=Posts&WeblogID=10928&WeblogPostID=10016587
also:
Team System Café:http://www.teamsystemcafe.net/Resources.aspxProgramming Windows Phone 7 Serieshttp://download.microsoft.com/download/E/3/5/E359FC51-1CF5-47F1-9BF3-74AB09D3339B/ProgWinPhonePreview.xps"How Do I?" Videos for Windows Azure Platformhttp://msdn.microsoft.com/en-ca/azure/dd439432.aspxIntroducing Windows Azure:http://download.microsoft.com/download/0/C/0/0C051A30-F863-47DF-BC53-9C3CFA88E3CA/Windows%20Azure%20David%20Chappell%20White%20Paper%20March%2009.pdfSilverlight Videoshttp://www.silverlight.net/learn/videos/silverlight-videos/#cat1
A comprehensive set of labs built by developers for developers, covering all blocks and advanced configuration scenarioshttp://blogs.msdn.com/agile/archive/2010/05/24/hands-on-labs-for-enterprise-library-5-0-and-unity-2-0-released.aspx