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She is portrayed by Rene Russo.
At the Metropolitan Museum of Art, an attempted robbery of precious paintings fails when museum employees discover imposters posing as staff. In all the confusion of locking down the museum and capturing the robbers, Thomas Crown slips into an adjacent room and steals the painting of San Giorgio Maggiore at Dusk by Monet. The insurers of the $100 million artwork send investigator Catherine Banning to assist NYPD Detective Michael McCann in solving the crime. In the beginning, the detective and his assistant make fun of Catherine for trying to find the thief. But, soon, Catherine proves that she's smarter and sharper than the detective in solving the crime.
In reviewing video of the rooms involved in both robberies, one of which was strangely "blank", Banning follows clues to discover how both robberies are connected. She quickly comes to suspect that the wealthy financier Thomas Crown is behind the theft. In the meantime, within two days of stealing the artwork, Thomas Crown, donates one of his own personal collections to the museum to be displayed in the same place where the stolen Monet painting was hanging. During the donation ceremony, he meets Catherine and while she accuses him of stealing the Monet painting, he immediately is attracted to her wittiness.
Banning is intrigued at his motivations and begins a game of cat-and-mouse to recover the painting. Despite the fact that both of them intuitively know what the other is up to, the two of them continue to meet in high class locations and intimate surroundings while Banning continues to search for the painting. On their first date, Catherine gets his blazer from him pretending to feel cold. Once she wears his blazer, she passes on his house keys to the police who immediately makes a copy of them. When he drops her off at her place, she slyly put his house keys back into his blazer. When Thomas tries to woo her, she asks him, "Do you really think that I'll sleep with someone that I'm investigating?".
The next day, she illegally enters into Thomas' house and searches for the painting. She presses a button under a table in his study and finds the Monet painting that was stolen from the museum. She triumphantly enters into the police station and asks to verify the authenticity of the painting taken from Thomas' house. Soon, they realize that it was a copy of the original. Angered at being outwitted by Thomas, she agrees to another date with him and they end up sleeping together. Afterwards, she continues to see him regularly and he takes her to his mountain house on a beach and they have a good time. When she returns from his mountain house, detective Michael shares with her photos of Thomas with another woman, Anna, just before and after his date with Catherine. When she sees the photos, Catherine immediately starts crying as she truly loves him.
The constant contact, matching of wits (and the romantic pursuit of Crown), cause Banning to fall in love with him. But her commitment to her job and her doubts about Crown's true intentions make her hesitate. Thomas, too, falls in love with her and is concerned about falling in love with a woman who investigates his crime and discusses it with his psychiatrist. When Catherine confronts him about Anna, he replies that he simply wanted to know if she's after the painting or is in really love with him.
To prove his love to her, Crown promises to return the stolen artwork to the museum before 4 PM the next day. If he can't do it, he asks her help in returning it to the proper place on the museum without anyone's knowledge. But, she refuses to help him return the artwork without anyone's knowledge. In her doubt, Banning betrays Crown's plan to Detective McCann who fills the museum with dozens of police officers in an attempt to catch him in the act. In the mean time, the police and Catherine figure out that Anna is in fact, the daughter of a famous German painter, Heinrich Knutzhorn, whom they suspect copied the Monet painting for Thomas. Catherine was fooled by the copy and took it from Thomas' house without his knowledge. Later, they realize that it was Anna who copied the painting for Thomas and who was waiting in his bed room to be paid by him for her work when Catherine visited him.
Around 3:40 PM, Thomas enters the museum amid several police officers in disguise and several others monitoring him on the surveillance cameras and immediately puts on a bowler hat. The police soon realizes that there are numerous men with bowler hats on and they can't identify Thomas from the surveillance video. Thomas throws a few tear gas shells into the room where the original Monet painting was hanging. The fire sprinklers start sprinkling water due to gas generated from the tear gas shells. Automatically, the iron doors in front of the valuable paintings start to shut to protect the paintings from water. However, the door in front of the painting that Thomas donated, which is hanging in the same place where the original stolen Monet painting was hanging was stuck and doesn't close. Water from the fire sprinklers spray on the painting that Thomas donated and it washes away the water color and the original Monet painting appears in the background. When a police officer checks what stopped the door from getting stuck, he picks up a pencil with the words, "Crown Acquisitions".
Soon, the police realizes what happened. Immediately after stealing the original Monet painting, Thomas had an artist paint another painting with water colors on top of it, and donated it to the museum within two days of stealing the original. However, they also realize that another painting is stolen from its place; one which Banning had previously expressed a desire to possess. Since the second stolen painting is insured by another company and her job is now finished, Banning's knowledge of Crown's plan allows her to meet him at a prearranged spot. Detective Michael is no longer in a mood to pursue Thomas as he's doing for a kick rather than money and he returns them anyway soon afterwards. Michael asks Catherine to convey his wishes for Thomas. When Catherine goes to the location, where she was supposed to meet Thomas, she encounters a man with a bowler hat instead and he gives her a bag with the newly stolen painting. She goes to the airport and asks the clerk to mail the painting to the police head quarters and catches a flight to go home in Britain, heart broken.
During the flight she cries as she truly loves Thomas and is heart broken because he didn't keep his word to go live with her. However, someone from her back set throws a towel and asks her to wipe out her tears. She looks back and sees Thomas Crown sitting behind her and she jumps over her seat to hug him and kiss him and tells him, "If I see you playing stunts again, I'll break both your arms".