Showbiz golden couple Jen, 51, and Brad, 56, wed in 2000 but divorced five years later.
Prior to their very public separation, Brad had an upcoming movie with Angelina, the action romance Mr. & Mrs. Smith.
That 2004 film - about a husband and wife's struggle to keep their marriage alive until they realise they are both secretly working as assassins - went down in Hollywood history.
The co-stars went on to get married but their 12-year relationship came to an end in 2016.
Ang claimed to have never met the Friends star but that, it appears, wasn't the real story.
“I was on the Friends lot and pulled over and introduced myself,” Jen told Vanity Fair .
“I said, ‘Brad is so excited about working with you. I hope you guys have a really good time.’”
But when the same question was put to Angelina by Vogue, her initial answer was no - and fans around the world couldn't work out why.
"But... so... you asked if I have ever met Jennifer and I said no," she later said.
"I did, but it was not a proper meeting. We've, like, passed each other and said hi briefly, shook hands. But not a real sit-down-and-talk kind of meeting."
She was then asked if she would be up for such a get together.
"That would be her decision, and I would welcome it," the star added.
She previously opened up about the tender moment that son Maddox first called Brad his dad.
The 44-year-old Maleficent star spoke about the heartwarming few seconds in a 2007 interview with Vogue.
The pair adopted Maddox, who is now 18, from an orphanage in Cambodia and Angelina was recalling the moment that he adjusted to his new parents and she realised that Brad had the potential to be a "wonderful father."
Speaking at the time, Angelina said: "He just out of the blue called him Dad. It was amazing.
"We were playing with cars on the floor of a hotel room, and we both heard it and didn’t say anything and just looked at each other."
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