Well, we all know what happened to that marriage, and after Brad's departure from their romantic union, Jen left Brad to run the production company solo.
But what about all of the projects the couple had in the pipeline?
Most of 'em went kaput, including the Untitled Jeff Buckley Film.
But with so many Hollywood heavy-hitters dying for the rights to the project, how did Brad and Jen woo the Buckley estate into handing it over in the first place?
"The only person Jeff's mother ever said yes to was Brad Pitt," the film's current producers, Michelle Sy and Orian Williams, tell us. "He was really kind to her and she appreciated that he wanted to make a movie inspired by Jeff's life."
And turns out it was Jen who inspired Brad to pursue Buckley in the first place.
"Jennifer Aniston actually introduced Brad to Jeff's music. She has always been a fan of his," the producers revealed to us. "But when they broke up, the project never came to fruition because it was part of their joint Plan B production company."
But don't worry, Robert Pattinson, Papa Pitt never wanted to play Buckley, he just wanted to produce the flick.
Apparently, Buckley's mama, Mary Guibert, who is the executive producer on the current film and in charge of who has access to her son's journals, photos and recordings, wasn't so thrilled with the majority of movie pitches telling her about her son's life, but she was smitten with Pitt.
"She was impressed that Brad took interest in her son's life and wanted to make a film about him for the right reasons and in the right way," explain the producers who took up where Pitt left off and now work closely with Mama Mary.
Unfortunately for Pittiston, the project, like their union, never worked out the way they had originally planned. The name "Plan B" is sounding a little ironic now, eh, kids?
Lucky for Buckley, sounds like his legacy is in good hands.