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Just call her Louis’ Girl! Academy Award-winning actress Angelina Jolie poses in debut campaign as the new face of famed French fashion house Louis Vuitton and its “Core Values” campaign.

In the ad, unveiled on the pages of Woman’s Wear Daily (WWD) Monday, Jolie’s sits sans makeup with a weathered, monogrammed LV Alto bag at her side. She was photographed by legendary photographer Annie Leibovitz aboard a wooden boat floating in a green marsh in Cambodia’s Siem Reap Province — an area the actress discovered during filming for her 2000 film Lara Croft: Tomb Raider.

“People are not used to seeing Angelina in this situation,” Vuitton executive vice president Pietro Beccari tells WWD of the makeup-free image. “I like the fact that it’s a real moment. This travel message we give through personal journeys is a fundamental one for the brand.”

In April, Jolie signed a lucrative deal with LV for what E! News snoops say will be a print-only campaign. Jolie will be paid “close to $10 million” for her work with the brand, a source familiar with discussions reports. The gig is expected to be the most lucrative endorsement deal of Angelina’s career. She’ll reportedly donate all proceeds from the Vuitton deal to charity.

Jolie’s three-year endorsement deal with St. John ended in 2010. The mother-of-six recently launched a jewelry line dubbed Style of Jolie.