Aniston also played down the world's fascination with the pair, as she told Entertainment Tonight on the evening of the very event: "It's hysterical but what else are they going to talk about?"
At the Los Angeles bash, Pitt accepted the award for Outstanding Performance by a Male Actor in a Supporting Role courtesy of his work in Once Upon a Time in Hollywood.
Showing his playful side, the 56-year-old noted the similarities between his onscreen role of Cliff Booth and his own life in a hilarious speech.
"Let's be honest. It was a difficult part," he said. "A guy who gets high, takes his shirt off and doesn't get on with his wife. It was a big stretch."
The joke regarding his former wife, Angelina Jolie, was met with a rapture of applause.
Of course, the camera shifted focus upon Aniston - who laughed along with her Hollywood peers.
But Pitt also made sure to show his support to Aniston, as she took home the award for Best Actress in a Drama Series courtesy of her role in The Morning Show.
Despite being backstage, Pitt reportedly "dropped everything" to watch her speech on the small screen.
We may only be a few weeks into 2020 but the great Pitt and Aniston reunion is without doubt our favourite moment of the year so far.