It depends a little on what they will be doing and what level they are.
Some modules I wish someone pointed out to me when I started are:
- StringIO - to stop them from reimplementing it, which they will if they don't discover it.
- logging - to put them on the right path when it comes to debug printouts
- pickle - to stop them from trying to use XML everywhere.
- xml.etree.ElementTree - To save them from the DOM model when they actually need to work with XML.
- pprint - to make nested structures in python less intimidating.