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Currently you are able to watch "Chuck" streaming on Amazon Prime Video. It is also possible to buy "Chuck" on Blockbuster, SF Anytime as download or rent it on SF Anytime online.
When Buy More computer geek Chuck Bartowski unwittingly downloads a database of government information and deadly fighting skills into his head, he becomes the CIA's most vital secret. This sets Chuck on a path to become a full-fledged spy.