During the first day of school at Constance Billard, Jenny takes her place as the new Queen Bee. However, Blair gets in her way. Lily returns home to find that things are not as they were when she left them with Rufus. At NYU, Olivia Burke, an actress, enrolls and is assigned to be Vanessa's roommate.

Vanessa, hoping to finally win her mother Gabriela’s approval, desperately vies with Blair for the honor of delivering the freshman toast at NYU, but at what price? Dan invites Olivia to meet Rufus and Lily, which leads to all sorts of problems for the new couple. Serena and Nate team up to help Carter Baizen.

In need of publicity for his new hotel, Chuck decides to move up his club’s opening and enlists Serena’s help to get the word out to her celebrity clients. Feeling left out of the planning, Blair attempts to win Chuck’s approval by secretly helping him with a problem concerning opening night. Dan is unnerved when he finally watches one of Olivia’s infamous sex scenes with co-star and real-life boyfriend at the time, Patrick Robinson. Jenny is forced to choose between her relationship with Eric and her new role as Queen Bee. Rufus gets Lily into the Halloween spirit.

Olivia says something she regrets during her appearance on Jimmy Fallon’s talkshow and tries to keep Dan from finding out. With election day around the corner, Nate suspects his grandfather will stop at nothing to get Trip elected to congress. In the midst of another feud with Serena, Blair befriends a new “it” girl and takes her to an election night party at Chuck’s hotel, hoping to make Serena jealous.

Jenny wants to be the Queen Bee of not only Constance but of all the Upper East Side, as she lands the hottest escort for the Cotillion. Meanwhile Dan and Vanessa try to convince Olivia to stay in NY by showing her the "true college experience". Leighton Meester's new single "Somebody to Love" is featured in the episode, along with performance from Plastiscines.

Hoping to impress the elitist theater kids at NYU, Blair sets her sights on landing a private concert with the hottest musical performer of the year, Lady Gaga. Dan and Olivia sign up to write and star in a school play, based on an idea by Blair and directed by Vanessa. With Blair out of the picture, Serena turns to Nate to help her get through a difficult situation. As a favor to Chuck, Jenny agrees to hang out with Damien, the son of an ambassador who is staying at Chuck's hotel, but the experience proves to be a lot more intriguing than she expected.