The £6.1m ($10m) paid to Jolie is thought to be a record for a single advertising campaign.
The global print ad campaign is set to launch this summer and celebrated photographer Annie Leibovitz will take the photographs, according to reports.
Jolie follows Jennifer Lopez, Madonna and Scarlett Johansson as previous ambassadors for Louis Vuitton's high-end products.
The shoot for the ad campaign will take place in the next two weeks, and the images will appear in newspapers and magazines around the world later this year.
Jolie, who is the partner of actor Brad Pitt, is known to be selective about endorsing products. Her most recent modelling contracts were for fashion company St John and cosmetic label Shiseido.
Louis Vuitton's payout dwarfs that of the £3.2m T-Mobile paid to Catherine Zeta Jones.
Louis Vuitton was unavailable for comment.