Well, there's already http://showMeDo.com which is really great. Covers lots of programming and related functions like using IDEs like Eclipse and editors like Vim. There's also tutorial episodes on design like suggested by a commenter before. No Photoshop or the rest of the Adobe CS suite however, all F/LOSS like GIMP and Inkscape. I'm actually practicing by learning from Eric Florenzo's playlist on Django here[1].…
Watching someone code is different, though. It's not prepared in advance, it doesn't have them trying to be a braggart and show you some clever thing they know, and you actually get to see their process as they go from idea to software.