Speaking to OK! Magazine on jobs he lost out on, he said: "If we were doing a show on the great movies I've passed on, we'd need two nights.
"I did pass on The Matrix. I took the red pill!"
He said: "The first movie star who says yes is Brad Pitt, he's doing Seven Years in Tibet and then he's coming out of it and he's like 'I'm way too exhausted to take this on,' so he's gone.
"Then we go to Leonardo [DiCaprio]. He says yes, we have meetings with him and then he goes, 'You know, I can't go do another visual effects movie having just finished Titanic' and he drops out. Then Will Smith joins it and he drops out."
Pitt now seems to look at the missed opportunity rather philosophically. When asked at Santa Barbara International Film Festival about iconic roles he'd passed up on, he said: "I'll give you one, only one, because I really believe it was never mine. It's not mine. It's someone else's and they go and make it. I really do believe in that. I really do. But I did pass on The Matrix."
Pitt is currently enjoying a pretty spectacular awards season, winning all sorts of gongs for his role in Tarantino's Once Upon a Time... in Hollywood, as well as being tipped for an Oscar next week.
He added: "It's really fun when your number comes up. I look at it this way, it's a kind of a wheel of fortune, and there's so much good work every year. It's so nice to see your friends go through this and then it's nice to be here myself. So I have a lot to be grateful for."
The 56-year-old actor also won a BAFTA at this year's show. He couldn't be there to accept it, so this presumably gave him licence to be a bit cheeky with his acceptance speech.
When Margot Robbie accepted his award for Best Supporting Actor, she read out his speech for him, which made references to two of the UK's most contentious topics right now: Brexit... and Prince Harry and Meghan Markle stepping down from their roles as senior members of the Royal Family.
Speaking on his behalf, Margot said: "Hey Britain! Heard you just became single. Welcome to the club!
"Wishing you the best with the divorce settlement."
That one was met with laughter throughout the auditorium, but Pitt didn't stop there.
Lifting the award up, Robbie continued: "He says that he is going to name this Harry - because he is really excited about bringing it back to the States with him."
A bit awkward, seeing as Prince William and Kate were in the audience.