Director Oliver Stone concurred with the choice, telling People, the "proportion of her face is beautiful.
"She's a great package, beautifully put together," he added.
Jolie, 30, is currently in Nambia with her boyfriend, Brad Pitt, 42, and their two adopted children awaiting the birth of their first child together. People said they also served as the "World's Most Beautiful Family."
People noted when Jolie is traveling as a United Nations goodwill ambassador or visiting disaster scenes around the world, she is typically low-maintenance and is never shy about appearing sans makeup.
Also making the "100 Most Beautiful People" issue were all 26 spokesmodels for NBC's "Deal or No Deal," "American Idol" host Ryan Seacrest; actresses Halle Berry, Julia Roberts, Scarlett Johansson and Kirstie Alley and actor George Clooney.
People's annual "Most Beautiful" issue comes out Friday.
Celebrity Families of 2014 [PHOTOS]