That's more about personal connections than the quality of life of a region, right? Granted, geographically if you happen to know those people it makes it hard to connect with them, but most people can't just ring up Guido when they have a Python question.
As far as real estate... I don't know about your specific situation but as a whole the valley is much more expensive than the Phoenix area. San Jose, through Cupertino, up to Mountain View... on average you're easily paying twice as much for the same square footage (I just checked San Jose on Zillow. 2,000 sq ft is easily 600k).
As far as Phoenix-based Python developers, there appears to be a Python meetup group, 'DesertPy': http://www.meetup.com/Phoenix-Python-Meetup-Group/
As far as real estate... I don't know about your specific situation but as a whole the valley is much more expensive than the Phoenix area. San Jose, through Cupertino, up to Mountain View... on average you're easily paying twice as much for the same square footage (I just checked San Jose on Zillow. 2,000 sq ft is easily 600k).