Unveiled Monday in Women's Wear Daily, Jolie's stark, beautiful new shot (with a weathered, monogrammed LV Alto bag at her side) was photographed by legendary photographer Annie Leibovitz who, according to WWD, had to shoo Jolie's elder four kids out of the picture frame to get her photo. 

“People are not used to seeing Angelina in this situation," Vuitton Executive Vice President Pietro Beccari tells WWD of the chill, makeup-free image. The 36-year-old star first discovered Cambodia in 2000 while filming Lara Croft: Tomb Raider, and is the birthplace of her eldest son Maddox, 10.  “I like the fact that it's a real moment, “ Beccari added. 

“This travel message we give through personal journeys is a fundamental one for the brand."  Jolie — was reportedly paid millions for the ad, which she'll donate to charity - joins other celebs who've already starred in their own  “Core Values"  LV campaign like Bono, Sean Connery, Keith Richards and Catherine Deneuve.