Milicevic was born in Sarajevo, Bosnia and Herzegovina, formerly Yugoslavia, the daughter of Damir, a homemaker and entrepreneur, and Tonka Milicevic, a slaughterhouse worker and entrepreneur. She has two younger brothers, Tomo Milicevic, (who is the guitarist in the rock band 30 Seconds to Mars), and Fillip. Milicevic, an ethnic Croat, emigrated to the United States with her family when she was five years old and was raised in Michigan. Miličević worked as a model while attending Athens High School in Troy, Michigan.

Milicevic began acting after graduation, with guest appearances in several television shows like Charmed, Seinfeld, Felicity,Nash Bridges, The Nanny, Buzzkill, Buffy the Vampire Slayer (as Riley Finn's wife and fellow black ops agent), Yes, Dear and Friends (as a mourner at Ross' memorial service on Season 9). Her acting career has also included a regular role on the HBO series The Mind of the Married Man.

In 2006, she starred in the CBS series Love Monkey. She was also in Just Like Heaven and Paycheck. She can be seen as Valenka in the James Bond film Casino Royale. She also had a role as Roxanne in Head Over Heels in 2001, she also played Stacey, in the 2003 hit Love Actually, appeared as Erika Helios in Frankenstein in 2004, in photos of Caroline in In Her Shoes in 2005, and as Jean Raynor in The Plague in 2006. In 2007 she played Lena, a model's older sister who would blackmail Daniel Meade after revealing that her "sister" is actually her teenage daughter after he slept with her on Ugly Betty. She also starred alongside with Paul Walker in Running Scared as Mila Yugorsky. In 2008, she starred in Witless Protection as well as a guest appearance in the House M.D. season 4 episode "House's Head".

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