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Currently you are able to watch "Chuck - Season 1" streaming on Amazon Prime Video. It is also possible to buy "Chuck - Season 1" on Blockbuster, SF Anytime as download or rent it on SF Anytime online.
The first season of Chuck introduced the series' main characters and established the general plot of the title character, Chuck Bartowski, having to adapt to his new life as a spy after the only remaining copy of the U.S. government's spy secrets are embedded into his brain. He is forced to juggle his responsibilities as a spy and the supervisor of a technical support team, called the "Nerd Herd", at his local Buy More store. Having become the most important asset of the U.S. government, Chuck is under the constant surveillance of his CIA handler, Sarah Walker, and NSA agent John Casey, who remind him that he cannot reveal his spy life to his sister Ellie, nor his best friend Morgan Grimes.