Great to see that MIT are addressing the most important problem with OCW: organizing the knowledge intelligibly.

I'm currently having fun with their introduction to programming that uses Python: http://ocw.mit.edu/courses/electrical-engineering-and-comput.... (Get the lectures on iTunes U.)

Granted, I don't know if that's the best gateway drug to programming, but it has the irrefutable advantage of assignments that apply the information. You always feel morose watching OCW lectures where the lecturer talks about an assignment that you'd love to do.