"You are sacred to me."
-Chuck to Raina, It-Girl Happened One Night
Chuck meets Raina when he suspects her father, Russell Thorpe, the CEO of Thorpe Enterprises, is planning buying Bass Industries. While their relationship is initially a friends with benefits situation, it later evolves into a romantic relationship. However, their relationship ends after Raina witnesses Chuck argue with his adoptive mother, Lily van der Woodsen.
Later, when Raina become interested in finding her absent mother and lets Chuck help; not knowing that he learned her mother was killed at the hands of his father, Bart Bass. He confides this to Nate, who is now dating Raina, and he tells her. Angry, Raina plans to ruin Chuck's life but stops when she learns Russell was really the responsible one. After he's arrested, she returns to Chicago with no bad feelings for Chuck.
In The Townie, Chuck discovers that Lily is planning to sell Bass Industries behind his back. After some intensive research, he decides that Russell Thorpe is the most likely to acquire the company and sets out to see him. When he arrives at the temporary New York office, he meets Raina; whom he mistakes for an assistant. She informs him that they are planning to buy the company and that the deal is set to close in 24 hours. Chuck later goes to see Lily, who explains that Bass Industries is in deep financial trouble and if they sell now they can control who buys it. She mentions that a private buyer has made a very generous offer and doesn't confirm or deny whether Russell is buying it. The next evening, they attend Russell's Return to New York party and Chuck asks him about the sale. Russell introduces Raina as his daughter and says that he had no idea Bass Industries was up for sale, or he would have bought it cheap and dismantled it for parts; as he hates the company after Bart stole it and kicked him out. Later, the original buyer backs out of the deal after Russell informs him that Chuck and Lily were at odds over the sale and Raina relays that information to Chuck. She asks him to come home with her, and he does (The Kids Are Not Alright).
Soon after, Nate's father, Howard Archibald, gets a job working with Russell. When Chuck learns about this, he asks Raina to have him fired as a favor but she refuses to do so. Russell later confronts Nate about him asking Chuck to get him fired and Nate answers that Howard can't risk going down in another scandal. Meanwhile, Chuck tries to apologize for asking Raina to fire Howard but she's lost interest in him. The next day, Howard pleads loyalty to Russell over Chuck to get his job back; which he does. Chuck goes to see Raina to apologize once again and she accepts (Damien Darko). Afterwards, he realizes that making Raina fall in love with him is the key to saving Bass Industries. In Panic Roommate, Chuck learns that Russell and his board are having their final vote that night on whether to acquire Bass Industries. Knowing he expects Raina to be there, he convinces her to spend time with him at The Palace Hotel, hoping to emotionally manipulate her into wanting to save it. They realize they have a shared experience of growing up in a hotel, since Chuck grew up at The Palace and Raina in one in Chicago. However, Russell shows while they're hanging out and reveals that Chuck knew about the meeting and kept her away on purpose. He admits to her that he did know about the meeting but now he's really starting to fall for her. Despite this, Raina isn't interested and says she can never trust Chuck again. The next day, Raina decides to give Chuck another chance after Blair Waldorf calls and vouches for him being a good man. Chuck vows to find another way to save Bass Industries that doesn't include putting Raina in the middle again.
The day before Valentine's, Chuck proposes a party to Russell; where he can show that the Bass name has equity. Russell agrees to put a hold on his plans for a 36 hours to give Chuck a chance. Meanwhile, Blair decides to shadow Raina for W Magazine, and Serena agrees to help her reel Raina in since her relationship with Chuck was just him using her anyway. However, Chuck tells Serena that his feelings for Raina are very real and he has a special surprise planned for her at the party. Not wanting Blair to get hurt, Serena convinces Raina to not do the piece. Later that day, Howard reveals to Chuck that Russell lied about putting his plans on hold; but that Bass Industries is more profitable kept whole so it makes no sense as to why Russell is planning to slice it up to sell. Chuck asks Raina why Russell hates his father so much, and Raina says it's because Lily was dating Russell but left him for Bart. As a way to prove loyalty to the Bass name, not Lily, Chuck has her fired from the Bass Industries board. At the party, Chuck reveals to Raina his surprise: an elegantly dressed room, which includes candles and a bed, inspired by Venice, Italy; where she was originally supposed to be that night but had to cancel. He tells her that when he cares for someone he isn't afraid to show it and they kiss, unknowingly seen by Dan Humphrey. Soon after, Lily confronts Chuck about having her fired and when Raina witnesses Chuck argue with her, she leaves angrily. Later that night, Blair ends up in Chuck's special room and sees Chuck try and convince Raina not to leave him because he really cares for her. However, Raina leaves anyway (It-Girl Happened One Night).
In While You Weren't Sleeping, Chuck asks Nate to "accidentally" bump into Raina and distract her until Chuck can meet up with them to convince her to give him another chance. However, Nate and Raina begin to have feelings for each other after spending the day together. Soon after, Russell obtains evidence of Lily's perjury and plans to blackmail the Bass family with it. However, Nate and Chuck are able to sneak Raina into the conversation and she realizes how wrong her father is being. After Raina is gone, Russell reveals to Chuck that Bart was the one responsible for his wife Avery's death, and he never told Raina that she was dead; only that she left him (Empire of the Son). After a Modern Royalty photoshoot, Raina realizes that without her father, she has no family and tells Nate that she plans to look for her mother (The Kids Stay in the Picture).
When Chuck learns she is looking for her mother, he tells Nate that Raina lives a high profile life and her mother could easily find her to contact if she was truly interested in a relationship with her. Realizing Chuck is right, Nate agrees to discourage her search. Meanwhile, Chuck has his PI, Andrew Tyler, research the fire Avery was killed in. Later that day, Raina finds a potential match for her mother and travels to New Jersey with Nate and Chuck to find out if it's her. They confront the woman but she admits that it's impossible for her to be Raina's mother since she never had a baby. Disappointed, Raina realizes it was a mistake to go looking. Meanwhile, Nate reveals to Nate the truth about what he knows and Andrew Tyler brings a tape over that confirms Bart's involvement in Avery's death (Petty in Pink). Later on, Andrew brings Chuck a letter that reveals that Avery and Bart were having an affair and Bart probably killed her after she decided to go back to Russell. Nate offers to help him tell Raina what they know but Chuck orders him to stay quiet. Despite this, Nate tells her anyway and she tells him to choose between her and Chuck. He chooses Chuck and leaves. Meanwhile, he learns Blair is about to become engaged to Prince Louis Grimaldi and drunkenly sets out to win her back. However, his efforts fail and Blair comes to The Empire to tell him that she is engaged. Upset, Chuck punches a hole in a glass window; terrifying Blair and causing Nate to realize he chose wrong (The Princesses and the Frog). The next day, Nate discovers that Raina has invited Chuck's evil uncle Jack Bass to town to take him down, but he teams with Jack and Chuck to destroy Russell. They inadvertently discover that Russell was really the one who set the fire that killed Avery because she was planning to leave him for Bart. Russell offers them whatever they want to prevent them from telling Raina, and Chuck tells him to leave New York forever and to never return. He agrees and plans to return to Chicago. Later that night, Nate realizes Raina is still planning revenge on Chuck and he tells her the truth about Russell. Devastated, she calls him to tell him to never contact her again. He mistakingly assumes Chuck went back on their deal and kidnaps Blair as revenge (The Princesses and the Frog). However, Chuck, Raina, and Nate track down their location and save Blair before having Russell arrested. Afterwards, Raina decides to return to Chicago (The Wrong Goodbye).