When Jen took the stage to accept her award, Brad was seen backstage, stopping everything to watch her speech on TV.
Brad poked fun at himself in his acceptance speech, sarcastically saying it was a "stretch" for him to play a man who walks around shirtless and doesn't get along with his wife.
The pair could be seen grinning as they crossed paths backstage, with Jen going in for a hug in one of the snaps of the pair together.
He told the audience: "When I started acting again and going to auditions again I'd always get to like the final callback and I think many people know what that's like. I now realize how fortunate I am to be a part of this community", he said with onstage after his name was called.
Brad Pitt makes his dating life the point of the 2020 award season.
DiCaprio is nominated for best actor at the awards show.
When Pitt accepted his award, he seemingly referenced his previous marriages, saying, "Let's be honest, this was a tricky half: A man who will get excessive, takes his shirt off, and would not get on along with his spouse. I don't know ... probably because of my personal disaster".
She told the crowd: "I was thinking back to when I was a little girl and I didn't have a VCR and I would tape Happy Days and listen and think I'm gonna get out of my house and do that one day".
Backstage, Pitt watched on proudly as she spoke of her beginnings as an actor, the footage promptly sending Twitter into overdrive. Pitt maintained that they were good friends on the Golden Globes red carpet.
Both Pitt and Aniston have actually been out and concerning throughout this year's honor program circuit on behalf of their tasks.
The camera then cut to a shot of Aniston, who clapped at the quip.