I watched the pilot episode of Chuck this evening. From the ads, it seemed like it was going to be a retread of the concept from Scarecrow & Mrs. King: professional spy and housewife team up, only with the genders reversed. However, it is not. Sure, the hot love interest is a kick-ass CIA agent (she really is cute, even if she is blonde, and played by a decent actress) and sure, the hero is a geeky everydude who works in the TV equivalent of Geek Squad at Best Buy (he is also played by a charismatic actor, thank goodness). However, the difference is that he has some kind of information that was downloaded into his head that makes him valuable to the government. I like the secondary characters as well, particularly the slightly amoral NSA agent, played by Adam Baldwin (aka Jayne, from Firefly). The geeky best friend is a wee bit annoying, but it's the first episode -- I'll give him time to mellow. I also like the concerned sister and her boyfriend, Captain Amazing. The show also makes a funny commentary on big stores. The hero works at "Buy More" and next door is "Large Mart," a riff on Costco. The sets are funny, because they take the real thing and make it slightly ridiculous. Heh. Social commentary. :)
All in all, I think I'd recommend it. I'll probably watch a few more and see if the writing is as good as the premise.