This is a great idea. It's much more personal than the stack sites and feels more like a mentorship set-up (a la big brother, big sister). I also think that the 1-to-1 connection is encouraging for askers: I oftentimes don't post to stackoverflow because I don't know if the question will ever be answered. At least there is a better chance of some form of life responding from the other end.

Well done. I hope to see it take off.