Xtreme Bean is quite possibly the best coffee shop in Tempe.
Yes I know the staff is eccentric, grungy and not super friendly but the prices are good and there is plenty of places to sit and chill, kind of like a coffee shop equivalent to a dive/neighborhood bar. I've been going there at least once or twice a week for 5-6 years and they know exactly what coffee drink I need. They have an excellent selection of teas, pastries and sandwiches.
My only beef is that it is always busy especially at night, but it sure beats going to Starbucks in my opinion.