Why do you think Sarah was instantly attracted to Chuck?
She admitted in season 3 that she basically was attracted to him from the first ep on. I think the key factor was Chuck's genuineness. Chuck was such an open person. I mean he never really tried to hide how he felt about Sarah and he wore his heart on his sleeve when it came to his emotions with regards to almost everything. Given that Sarah was so used to lying and deception while in the CIA and before that with her father, it was difficult for her to deal with someone who was someone who was so open and genuine to her. I mean Chuck basically opened up his entire group of family and friends to her. The key thing you can see is in the individual scenes between them when Chuck would admit how he felt about her, what his hopes and dreams were etc... and you could tell that Sarah could barely hold it together because she was not used to dealing with that level of openness and honesty.
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