For people looking to start Chuck or are already watching, just want to tell you that the finale of season 4 would be more satisfying (as a series end) if you would just stop watching there. The quality goes down a lot in season 5 and they do some things which you will not like if you liked the series till season 4.
Infact the season 4 end is probably a perfect series finale and 5 was possibly unwarranted.