Here is a list of web sites that offer some training / tutorials on Expression Web.

http://expression.microsoft.com/en-us/cc136522.aspx
http://www.learnexpression.com
http://expression-tutorials.com
http://by-expression.com
http://any-expression.com
http://www.expression-web-designer-help.com
http://www.homepagedoctor.com/ExpressionTutorials/Tutorials.htm