She received an Emmy nomination for the 1999 TV movie Joan of Arc, and two Golden Globe nominations for Joan of Arc and the 2001 TV movie Uprising.

Sobieski was born in New York City. Her mother, Elizabeth Sobieski (ne Salomon), is an American film producer and screenwriter who also works as Sobieski's manager, and her father, Jean Sobieski, is a French painter and former actor. Sobieski has a younger brother, Robert.

Sobieski's first name, "Liliane", was the name of her paternal grandmother. One of her middle names, "Elsveta", is derived from "Elbieta", which is the Polish equivalent of "Elizabeth".Her father is of Polish and Swiss ancestry. Her maternal grandfather, United States Navy captain Robert Salomon, was Jewish, and Sobieski grew up in a "pan-religious" family; she has said that she is "proud of [her] Jewish roots".She graduated from Trevor Day School in 2001 and studied literature and fine art at Brown University.

Sobieski was spotted by a talent scout who noticed her while he was scouting the cafeteria of a New York City private school. After that encounter, she became a candidate for the role of Claudia in Interview with the Vampire (1994), which she eventually lost out to Kirsten Dunst. She portrayed the character of Anna Yates in the 1994 TV movie Reunion, which starred Marlo Thomas. Next, she played a lead role in A Horse for Danny, a made-for-television film which was released in 1995. Later, she had a major role in the comedy feature film Jungle 2 Jungle, with Tim Allen. In the film, she played the daughter of Martin Short's character.

She rose to fame in her mid-teens with her appearance in the movie Deep Impact (1998).The film was a major financial success, grossing over $349 million worldwide on a $75 million production budget. Deep Impact brought her to the attention of many casting directors. That same year Sobieski appeared in the Merchant Ivory film A Soldier's Daughter Never Cries. Sobieski's performance received praise from the critics; Emanuel Levy of Variety wrote that "the graceful Sobieski registers strongly as a potential star, combining physical charm with technical skill."The film also garnered her a Young Artist Award nomination, as well as a nomination by the Chicago Film Critics Association.

In 1999, she was cast as a supporting role in the teen comedy feature Never Been Kissed, which was starring Drew Barrymore. Sobieski also played a modern Lolita in Stanley Kubrick's Eyes Wide Shut. The film opened to generally positive reviews, but it generated several censorship controversies due to the explicit nature of its sex scenes. Recalling acting alongside Tom Cruise, she said he was "very kind and considerate with me," and says her most vivid recollection of Stanley Kubrick was that he "genuinely seemed to hold something magic". The title role in the TV movie Joan of Arc (1999) earned her an Emmy nomination and a Golden Globe nomination, and she became the youngest actress ever to portray Joan of Arc in a movie. She received a second nomination for a Golden Globe for her portrayal of Tosia Altman in the 2001 TV movie Uprising. In 2000, Sobieski was a part of the cast of the film Here on Earth, for which she received a Teen Choice Award nomination.

In 2001, Sobieski played the lead role in the road horror film Joy Ride with Paul Walker and Steve Zahn. The film received several favorable reviews. Garth Franklin of Dark Horizons stated that Sobieski "does a better job than usual".

That same year, she was cast in the thriller The Glass House, in which she appeared alongside Diane Lane. The film was panned by critics, and had a disappointing weekend $5,738,448 gross with little promotion. My First Mister, a low-budget drama, was also released in 2001. Sobieski's performance in the film was praised by critics, with Pete Croatto of Filmcritic.com writing that "As for Sobieski, who I've always liked, she does another fine job. This time it's with a shaky character the troubled Goth chick", and "Sobieski finds her character's human touch and runs with it.

Sobieski landed a starring role in the independent film L'Idole (2002), which opened at the Toronto International Film Festival. She then starred alongside John Cusack in the drama feature Max. She portrayed the character of Cecile in the miniseries Les Liaisons dangereuses (2003) with Catherine Deneuve and Rupert Everett, an adaptation of Laclos's classic novel of sexual intrigue made use of her fluency in French. She portrayed the role of Deianira in Hercules, a television miniseries which was premiered on May 15, 2005.

Sobieski speaks fluent French, which she learned from her father, who currently lives in France.

In January 2009, Sobieski began dating fashion designer Adam Kimmel. Kimmel is the son of American real estate developer Martin Kimmel and grandson of American boat racer and designer Donald Aronow. They were engaged on May 28, 2009 but chose to keep the news private. It was made public June 23, 2009, when fans at the premiere of Public Enemies spotted that Sobieski was wearing an engagement ring. The couple officially announced their engagement on July 17, 2009. Their daughter, Louisanna Ray Kimmel, was born in December 2009.

During an interview, Sobieski spoke about her views on having happiness and a positive attitude: "I think that happiness is a very strange thing. And we really feel that we have a right to this happiness. But I feel like it's constantly fluctuating, and that you can make yourself happy. I think it's an outlook. Having a positive attitude probably sounds like a corny thing to say, but a positive attitude really helps, and respecting your job really helps, and having the support of your family and friends really helps."

Sobieski, in a 2001 interview with IGN, spoke about her thoughts on if the movies she was doing were escapist or that they had a message for society: "Joy Ride isn't a film you would make a statement with. It's a fun, jump out of life film. That's great. I love those films. Those films are great in times like these too. You can make a point with a film and help society or not. Take a film like Bulworth, a fantastic film. There are certain films like that, that can appeal to everybody and have a message in it and that's really great."

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