Earlier this year the folks at Automattic launched www.WordPress.tv, which is a new website to learn about all things WordPress. I just had a quick look and it looks like the list of videos is quite extensive (Click the how-to link for the list of videos. Personally I’m not sure this tab is appropriately labeled, but hey, I found the list.) The site also has a WordCampTV section where you can watch videos, slides and listen to audio clips.
This site is definitely worth bookmarking and investigating further.