The actress will be dressed in Vuitton and feature in the clothing line's advertising campaign next year.
She follows in the footsteps of 'Lost in Translation' actress Scarlett Johansson and Jennifer Lopez.
The first ad will appear throughout the world in February 2005 will show the 'Pulp Fiction' star carrying the brand's new Manhattan bag.
Marc Jacobs, artistic director of Louis Vuitton, said: "The idea was to present this ultra-feminine woman and to show her in a rough and bare industrial environment, to dress her in a sophisticated way, opposite to the unexpected decor made of cement and concrete."
It is unclear if Thurman's deal will match that of Lopez, who was reported to have signed a £2m deal last April.
Louis Vuitton, which is owned by French holding company LVMH, has also used actress Chloe Sevigny and models Kate Moss and Naomi Campbell in its past promotional work.
Thurman, star of Quentin Tarantino's martial arts movie 'Kill Bill' and 'Kill Bill Volume 2', was dropped as the face of L'Oreal-owned luxury cosmetic brand Lancome in October 2003 after just two years.
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