Thornton gets candid in a new interview with Playboy, on newsstands Nov. 22, and says he would love to work with Pitt in the future.
... And he already has some roles in mind.
"This might surprise people, but I'd love to do a movie with Brad Pitt," the 61-year-old actor says. "I think we'd be great together. We'd play a couple of Southern guys."
Thornton -- who recently exclusively told ET that he and Jolie are still "good friends" despite their 2003 divorce -- also has nothing but positive things to say about his ex-wife.
"She's a great person," he says about Jolie. "And she's one of the people who didn't abandon me. She never has."
ET spoke to Thornton at the press junket for his latest film, Bad Santa 2, in Los Angeles on Friday, when he gave us an update on how Jolie has been holding up since her and Pitt's shocking breakup.
"She seems, you know, OK to me when I talk to [her]," Thornton said. "I don't talk to her that often though. You know? We're still very good friends. But she's got her world. I've got mine."
"When people are going through their trials and tribulations I try to leave them alone unless they want to talk to me," he added.
However, he did make it clear that Jolie can still count on him anytime for support.
"Of course," he sweetly replied when asked if he'd be there if she calls.
Thornton and Jolie tied the knot in 2000 after meeting on the set of their film, Pushing Tin. They separated two years later, and officially divorced in 2003.
No word yet if Pitt is open to a Thornton collaboration, though the 52-year-old actor was all smiles promoting his latest film, Allied, in China on Monday. A svelte Pitt looked handsome in an all-black outfit, and happily signed autographs for 40 minutes for fans.