While coping with the realization that Sarah still has feelings for Bryce, Chuck must assume his toughest cover yet by going on a mission as Sarah's husband. The team must foil the plot of a politically connected counterfeiter, who may be endangering the lives of Anna, Morgan and Anna's parents. Both Morgan and Anna also find themselves in the cross hairs.

At a BioScience conference, Chuck runs into Jill, his ex-girlfriend who broke up with him and later dated Bryce Larkin. He flashes on her boss, Guy Lafleur, who is suspected to be working on biochemical weapons. Chuck is ordered to reconnect with Jill in order to gain more information on Lafleur. Meanwhile, Emmett wants the staff to take CPR lessons including a test.

Chuck, Sarah and Casey learn about a man called “Perseus” who is behind Fulcrum’s plans to build their own Intersect. While Sarah and Casey are sent to find Perseus, Chuck and Agent Cole Barker are forced to stay in a safety bunker. When the mission takes a dangerous turn, their orders to stay out of harm’s way go out the window. Meanwhile, Morgan tries to convince Anna that moving in with him would be a bad idea.

When Awesome is mistaken for a super spy by the evil Sydney Price, Chuck must become his handler and show him the spy ropes. While on a mission for The Ring, they meet the mysterious Daniel Shaw. Meanwhile, Morgan gets promoted to assistant manager and must deal with Jeff and Lester's latest hijinks.

Chuck learns that his latest solo mission will be a final test to see if he is ready to be a spy. Chuck needs to put everything he has learned into action to avoid going back to his old life while Sarah and Shaw observe his every move.