I'd call Chuck good TV. Funny, witty, and fully embracing of its own hokeyness. Good old fun. (I'd reference you to Season 1 of Heroes). It's balanced pretty well between being episodic (ie, Law and Order) and advancing a central story line (ie, Lost).

Despite that, know going in to it is that it's fully a boy show. Lots of guns, lots of women in lingerie. Also, its first few episodes are a little weak. Like 30 Rock, the show takes a little while to find its way. But once it does, it gets good.