I'd start with python or javascript these days (I personally did my first self taught hacking in basic on DOS -- some simple text processing for a statistics class). I think the learner resources might be better for python. If he doesn't know anything about programming then you might not be allowing enough time on the different technologies, that's pulling together a lot for a first project.

If you have a modern enough browser you might be able to keep it to html/css/javascript and use web storage for a database. That'd be good for some little single user system or browser based game or something.

Depending on the type of person he is and what you work on at your dev shop you could get him to fix real-but-small problems -- language in error messages, pixel level interface visual problems, etc.