Here are two great webcast series from some of my teammates. Lots of good information here - these guys really know their stuff.
Ron Cundiff presents the VB Soup-to-Nuts series. He's already introduced key aspects of the language, covered what the VB Express product does for you, and delved into Class Libraries. Hope there's plenty more to come, Ron!
Bill Steele presents the C# Soup to Nuts series. He's a bit ahead of Ron in his series, having started back in November, but there should be a lot of life left in the series.