Gold Bar has been a rallying cry for years in Tempe against the homogenized corporate vibe emanating from, among other places, the Starbucks a few doors down. It's on the smaller side and feels very intimate. It's a lower-energy scene than Xtreme Bean across the street (though they sometimes have live music), but a great spot to read, work, or hang out - the best for miles around, I'd say. If you're looking for something fun to do, they have a stack of games in the back.
You can't go wrong with their chai, mochas, or black coffee.