Which film first featured Brad Pitt and Angelina Jolie as co-stars?

Mr. & Mrs. Smith first featured Brad Pitt and Angelina Jolie as co-stars.

The 2005 action-comedy film stars Pitt and Jolie as John and Jane Smith, a married couple who discover that both secretly work as assassins for competing organizations. Doug Liman directed the film, which combines domestic comedy with elaborate action sequences.

Pitt and Jolie met during production, while Pitt was still married to Jennifer Aniston. Pitt and Aniston divorced in 2005, and Pitt and Jolie later became a couple. Their relationship made the film a frequent subject of celebrity coverage, although the movie itself was conceived as a fictional action story rather than a romance based on their lives.

The pair reunited onscreen in By the Sea, released in 2015. That film was written and directed by Jolie and explored a troubled marriage, making it notably different in tone from Mr. & Mrs. Smith.