As the summer is drawing to a close, Blair and Chuck are madly in love and adjusting to their new "in a relationship" status, breaking all the traditional rules of dating as would be expected. Serena returns from her European adventure with many secrets to hide and a complicated relationship with Carter Baizen. Nate returns from his travels with a mysterious brunette, Bree Buckley in tow. Rufus, Dan and Jenny spent the summer in the Hamptons, adjusting to the van Der Woodsens' glamorous lifestyle surprisingly faster than any of them expected. Meanwhile, Vanessa begins...
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. As Serena prepares to depart for Brown, she and Chuck have a major falling out, so she recruits Chuck's enemy, Carter, to help her get even. Nate and Bree decide to explore their relationship further, knowing full well that it could cause tension between their families who are political rivals.
It's 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 isn't quite right with Scott.
On the first day of school at Constance Billard, Jenny is forced to make her rightful place as the new Queen Bee of the Mean Girls. Unfortunately for Jenny, Blair is more than happy to intervene when news reaches her that Jenny may need her help. Meanwhile, Lily finally returns home to Rufus and her family to find that things are definitely not as she left them, especially after learning that Serena has decided against going to Brown University. Elsewhere, a famous teenage movie actress, Olivia Burke, enrolls at NYU and is assigned as Vanessa's new roommate in which ...
Lily and Rufus decide to move up their wedding to the next day, but a series of complications threaten to tear them back apart again. Meanwhile, Chuck discovers a secret that Carter has been keeping from Serena which involves Nate's girlfriend Bree and her family whom are out to get Carter. Dan and Vanessa are pulled into one of Georgina's schemes when she threatens to ruin Lily and Rufus' wedding by revealing the secret about Scott Rosson as their illegitimate son. Also, Blair is suspicious of Bree and shares her concerns with Nate that she may have an agenda ...
Vanessa and Blair both take to scheming to be given the honor of giving the freshman toast at NYU. Meanwhile, Serena and Nate try their hand at poker in hopes of winning Carter back from the Buckleys, and Dan wants to introduce Olivia to Rufus and Lily.
Chuck decides to move up his hotel nightclub's opening and enlists Serena's help to get the word out to her celebrity clients for publicity reasons. Feeling left out of the planning, Blair attempts to win Chuck's approval by secretly helping him with a problem concerning opening night. Meanwhile, Dan is unnerved when he finally watches one of Olivia's infamous simulated sex scenes in one of her movies with co-star and real-life boyfriend at the time, Patrick Robinson. Jenny is forced to choose between her friendship with Eric and her new role as Queen Bee of Constance...
Olivia says something she regrets during her appearance on Jimmy Fallon's TV talk show and tries to keep Dan from finding out. With the local election day around the corner, Nate suspects that his grandfather will stop at nothing to get his cousin 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.
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. Meanwhile, 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.
As Thanksgiving draws near, Blair suspects her mother, Eleanor, has been keeping a big secret from her, but it turns out to be something else entirely. Meanwhile, Vanessa is supposed to spend Thanksgiving with her parents, but has a fight with her picky and estranged mother and she ends up going to Dan's loft. Rufus discovers that Lily has been lying to him about the true nature of her mother Cece's health. Chuck tells Nate that he has some potentially damaging information about one of their friends: Serena whom is caught in a compromising position with Trip ...
On the anniversary of Bart Bass' death, Chuck wrestles with the dilemma of following his conscience, or that of his father. Serena begins to suspect in Trip, when thank Nate, discovers that has been joined by Maureen. Dan and Vanessa attempt to navigate their newly complicated friendship. Eric and Kira make work his plan to dethrone Jenny. Meanwhile, the relationship between Lily and Rufus deteriorates when he discovers the letter from Serena's father.
Nate and Serena decide to explore the boundaries of their friendship. Blair suspects that Chuck is having problems forgetting about the woman he saw at his father's grave. Jenny agrees to accompany Damien to a State Dinner, but she realizes that his plan is ruined by a memory of the school. Dan tries to overcome the confession of love for Vanessa, without any result. Rufus returns from a ski trip and tries his best to avoid Lily.
Rufus and Lily grow suspect of Jenny's relationship with Damien. Chuck learns more about the woman who may or may not be his mother. Dan and Vanessa struggle through the awkwardness of dating other people.
Despite being grounded, Jenny continues to see Damien who tells Jenny that he wants to have sex with her. Lily thinks to tell the secret that she has supported conceal, but after a call, she changes of mind. Dan and Vanessa explore a new stage of their friendship. Chuck is forced to make an extremely difficult decision about his hotel. Meanwhile, Serena and Nate have a fight that is reminiscent of past events.
Chuck finds himself once again at odds with his uncle, Jack Bass. Eleanor puts Blair in charge of making sure her latest fashion show is a huge success with an important client. Rufus attempts to get Jenny back on track by volunteering to have her help with Eleanor's fashion show, but the opportunity takes a big turn for the worse when Jenny learns that Agnes will be one of the models.
Chuck and Blair are faced with the most difficult decision they have ever faced as a couple. Serena plans a surprise birthday party for Nate, but Jenny does her best to sabotage Serenas's efforts. Dan and Vanessa's new relationship hits a bump in the road.
Chuck offers to throw a wedding for a very pregnant Dorota who insists that she and Vanya have a traditional wedding before her parents arrive from Poland and find their daughter pregnant and without a husband. Dorota asks Blair and Chuck to be part of the ceremony and walk her down the aisle. Serena tells Nate she is having breakfast with the Humphreys when in reality she's secretly meeting up with Carter Baizen. Rufus discovers that Lily has been lying to him about her whereabouts.
When Lily's ex-husband, Dr. William van der Woodsen, shows up unexpectedly in Manhattan, Serena finally gets the reunion she has so desperately wanted with her father, but the circumstances turn out to be far from ideal. When Serena and Nate continue to have relationship issues, a scheming Jenny is more than happy to be a shoulder for Nate to lean on. Meanwhile, Dan finds out that he didn't get accepted into the Tisch writing program and Vanessa admits she may have been somewhat responsible.
Will's return to the Upper East Side continues to stir up problems for Serena, Lily and his long-standing rival, Rufus. Serena and Jenny's relationship is strained as a result of Jenny's deception. Blair spends time on the Columbia campus and realizes where she truly belongs. Dan learns that Vanessa has been keeping yet another secret from him.
When things get tense between Rufus and Will, Serena chooses to stand behind her father, while at the Rufus is made to feel like an outsider in his own family. Meanwhile, Jenny deliberately shares information with Will that may ultimately destroy Lily and Rufus' marriage. After many failed attempts, Chuck makes one last grand gesture to reconcile with Blair, hoping she will finally accept the fact that they are destined to be together.
Blair must decide whether to meet Chuck at the top of the Empire State Building or risk losing their future together. A Gossip Girl gossip bomb involving Dan explodes Serena and Nate's relationship. Dorota and Vanya welcome their baby. Jenny hits rock bottom. Georgina returns to the Upper East Side...and she has an agenda.