Kurylenko was discovered by a female model scout while on vacation in Moscow at the age of 13. When she was 17, she signed a contract with the Paris-based Madison modeling agency. By the age of 18, she had appeared on the covers of Vogue and Elle. While working as a model in Paris, Kurylenko supported her mother in Ukraine.
She also appeared on the covers of Madame Figaro and Marie Claire.
She became the face of Triumph lingerie, Lejaby lingerie, Bebe, Clarins, and Helena Rubinstein, Furthermore, she modelled for Roberto Cavalli and Kenzo, and appeared in the Victoria's Secret catalog.
Kurylenko's first acting appearance was in Seal's music video, 'Love's Divine' in 2003, but her film career began in France during 2005. She received the certificate of excellence award at the 2006 Brooklyn International Film Festival for her performance in L'Annulaire, and also starred in the Paris, je t'aime segment Quartier de la Madeleine opposite Elijah Wood. That same year, she was selected to be the face of Kenzo's new fragrance, Kenzo Amour. She has appeared in all subsequent Kenzo Amour ads. In 2007, Kurylenko starred in Hitman alongside Timothy Olyphant. She had a minor role in Max Payne as Natasha. She played Bond girl Camille Montes in the 2008 James Bond film, Quantum of Solace. In the film she plays the role of a Bolivian Secret Service agent named Camille, who teams up with James Bond to avenge the death of her parents.
Kurylenko was featured on the cover of the December 2008 issue of the US edition of Maxim and on the cover of the February 2009 issue of the Ukrainian edition of Maxim magazine.
The fact that she is the first Bond girl from a post-Soviet state received mixed reactions in Russia. The Saint Petersburg based Communist group KPLO has accused her of "moral and intellectual betrayal" in starring in a film about the "enemy of the Soviet people" (meaning James Bond). In Ukraine the then-mayor of Berdyansk suggested naming a street after her in early 2008, and Kurylenko and her mother met Ukraine's First Lady Kateryna Yushchenko in President Yushchenko's family country house.
Kurylenko will appear in Terrence Malick's sixth feature, shot in fall 2010 in Bartlesville, Oklahoma. Also starring Ben Affleck, Javier Bardem and Rachel McAdams, the film is currently in post-production. She will also appear in Oblivion (2013 film), an sci-fi project starring Tom Cruise and directed by Joseph Kosinski.