But it seems meeting legendary boxer Muhammad Ali brought out the fan in the 34-year-old who couldn't resist giving him a cuddle after being introduced to him at a Unicef charity ball.
Muhammad Ali, actress Angelina Jolie, and actor Brad Pitt
Hug it out: The actress dived in for a cuddle with the former boxer
Beaming at partner Brad as she cosied up to the Parkinson's sufferer, 67, the Changeling actress looked like any other admirer delighted to meet her idol.
Initially, the couple just shook hands with Ali and his companion.
But after after a lively chat, the foursome got on so well that mum-of-six Angelina leaned in to give him a cuddle.
Muhammad Ali, actress Angelina Jolie, and actor Brad Pitt
Star struck: The couple were thrilled to meet Muhammad Ali and his companion
Muhammad Ali
Tactile: Angelina shared the affection around
The superstar couple both looked delighted to be on a night out together and were tactile and affectionate throughout the Beverly Wiltshire event in Los Angeles.
Revelling in an evening off parent-duty, they stole romantic moments at every opportunity and didn't leave each other's side at the star-studded event.
Their public displays of affection follow a newly released unauthorised biography claiming there are 'irreparable tensions' in the couple's relationship.
It was clear that the Hollywood couple remain unshaken by the allegations made in Ian Halperin's new book, Brangelina: The Untold Story of Brad Pitt and Angelina Jolie.
'They've broken up so many times it would make your head spin,' the author claims, declaring the couple will break up by 'Christmas 2010.
Brad Pitt and Angelina Jolie
Show of unity: Angelina Jolie and Brad Pitt cosy up at a UNICEF ball at the Beverly Wilshire in Los Angeles last night
But there was no sign of disunity between the two last night.
Angelina, a UNICEF ambassador, was seen gazing adoringly at her 46-year-old partner of five years and at one point ran her fingers through his hair.
And while all eyes were on the couple, they were not the only celebrities present.
A host of stars attended, including George Clooney, Matt Damon, Bruce Willis and Cindy Crawford.
The evening was designed to honour individuals who made key contributions to UNICEF's mission to save and improve children lives worldwide.
Producer and long-time philanthropist Jerry Weintraub was honored as Man of the Year with UNICEF's Danny Kaye Humanitarian Award.
The evening raised more money for the organisation than any UNICEF Ball to date.
Weintraub, Pitt, Clooney, Damon and Don Cheadle allo donated $250,000 to help the organisation's mission to reduce the number of preventable deaths of children from 24,000 to zero.
Weintraub directed the actor's in Ocean's Eleven and it's follow-up franchise.
Other guests included Joan Collins, Larry David, Selena Gomez, Benji Madden and Joel Madden and Alyssa Milano.
Joan Collin
Larry David
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