The two were among attendees at the annual Golden Globes foreign-language seminar on Saturday at the Egyptian Theatre in Hollywood, where directors nominated in the category discussed this year's competition.
The entries include Jolie's "In the Land of Blood and Honey," about family strife and abuse of women in Bosnia, and Almodovar's psycho-thriller "The Skin I Live In."
Unlike other celebrities at the event, Jolie surprised reporters by showing up early, relaxed and gracious as she posed for photographers and talked about what inspired her to move behind the camera for "Blood and Honey."
At one point, Jolie half-joked to a Spanish reporter that she was angry with Almodovar because he'd yet to hire her for a role. When Almodovar was given that news by an Associated Press reporter – within earshot of Jolie – the actress jumped into the fray.
"I am right here," Jolie noted. "Yes, because you have never given me a job."
"Oh my God," said a flustered Almodovar. "No, no don't worry, you are joining now. Absolutely."
"So one day," Jolie responded, "when all these cameras are gone, we find a film together."