As the summer draws to a close in the Hamptons, Serena and Nate have everyone fooled into thinking they are a couple to cover up the fact that Nate has been hooking up with a married, older woman. Blair returns from abroad with a hot guy on her arm, making a very jealous Chuck question his decision to leave Blair stranded at the heliport. Dan has spent the summer assisting a famous author. While interning for Eleanor Waldorf's company, Jenny sneaks an invite to a much-coveted Hamptons' White Party at which Eric introduces her to socialite Tinsley Mortimer.

In a humorous twist, Blair questions the lack of passion in her relationship with Marcus, while at the same time Chuck appears to have lost his "passion" for any woman other than Blair. Meanwhile, Nate struggles between his feelings for Vanessa and his more-complicated-by-the-day relationship with Catherine. Jenny risks losing her internship when Eleanor catches Jenny critiquing one of the Eleanor Waldorf designs.

In the midst of Fashion Week, a furious Blair learns that her mother, Eleanor, at the suggestion of her protege Jenny, has given Serena and her new socialite friend, Poppy Lifton, front row seats to the Eleanor Waldorf show. Hurt once again by Serena's popularity and her mother's betrayal, Blair decides to sabotage the show. Meanwhile, Dan starts hanging out with Chuck, but a walk on the dark side always has its risks and Dan learns that the hard way. Lily learns a secret that her new husband, Bart, has been keeping from her.

After Blair and Serena get into a catfight, Serena decides to get even with Blair, who has always dreamed of attending Yale, by ditching her plans to visit Brown, and instead accepting the Dean of Yale's personal invitation to visit the school. After discovering that none of his recommendation letters for Yale were ever submitted, Dan frantically tries to figure out a way to salvage his chances of getting into the school. While on the Yale campus, Chuck is kidnapped by a group of Skull and Bones members and Nate hooks up with a co-ed.