As the summer is ending, Blair and Chuck are madly in love and adjusting to their new "in a relationship" status, breaking all traditional rules of dating as would be expected.
Blair, who is determined to maintain her Queen status in college, embarks on her first day at NYU, along with Dan and Vanessa. Unfortunately, Georgina turns up as Blair's roommate in the dorms, determined to make Blair a social outcast.
It is an Upper East Side face-off when Blair and Chuck both set their sights on a particular item up for bid at Sotheby's and the personal stakes are high. Serena suspects that Carter may be up to his old habits. Georgina takes an interest in Dan, and Vanessa begins to suspect that something is not quite right with Scott.
It is the first day of school at Constance Billard, which means it is also time for Jenny to take her rightful place as the new Queen Bee. Unfortunately for Jenny, Blair is more than happy to intervene when news reaches her that she may be needed back at Constance.
Lily and Rufus decide to move up their wedding to the next day. Chuck discovers a secret that Carter has been keeping from Serena. Dan and Vanessa are pulled into one of Georgina's schemes. Blair is suspect of Bree and shares her concerns with Nate.
Vanessa, hoping to finally win her mother Gabriela's approval, desperately vies with Blair for the honor of delivering the freshman toast at NYU. 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.
Olivia says something she regrets during her appearance on Jimmy Fallon’s talk show and tries to keep Dan from finding it 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.
Not satisfied with just being Queen of Constance Billard, Jenny sets her sights on becoming the Queen of all the Upper East Side by landing the hottest escort for Cotillion. Nate and Chuck plot to help Serena and Blair repair their damaged friendship. Dan is upset when Olivia contemplates leaving school for a movie project.
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.
It wouldn't be Thanksgiving on the Upper East Side if there wasn't a serving or two of some major drama for the holiday. Blair suspects her mom has been keeping a big secret from her, but it turns out to be something else entirely.
On the anniversary of Bart Bass' death, Chuck wrestles with an issue from the past and a serious car accident rocks the Upper East Side. Dan and Vanessa attempt to navigate their newly complicated friendship. When Jenny is accused of beating up one of her classmates, Eric is faced with a tough dilemma.