I have purchased two bicycles from this company - a hybrid 2001 (University Drive location) and a city bike in 2013 (Rural Road location). I'm extremely happy with their selection, prices, and service. The most important factor in this rating is that the staff/manager went far above and beyond the call of duty to remedy a problem I had in ordering a bicycle. Whereas many companies will shirk responsibility when they make a mistake, TB demonstrates true customer service excellence.
They're really knowledgeable and patient, too. I'm bike-stupid (umm which one is the gear shift again?), but the staff never makes me feel that way. Unlike some other bicycle shops I've visited - where mean hipsters in fixies just glare at you condescendingly without offering a helping hand until you feel so awkward you walk out - Tempe Bicycle takes the time to explain the ins and outs of their products and make recommendations. And they don't just recommend the most expensive products; I came in looking to spend $100 on a lock and they convinced me to purchase a less expensive product b/c it would meet my needs (securing a child trailer in this case).
Final note, whenever I've had problems or help with my bike (remember my Bike IQ is like 10) they take good care of me without emptying the bank account. So if you're just a normal person looking for an awesome bike from nice people who know what they're talking about, look no further than Tempe Bicycle.