In 2006, then partners Angelina Jolie and Brad Pitt sold photos of their newborn baby Shiloh to People for a whopping $7 million—and then, in what would be come a characteristic move, donated it to charity. And yet, that wasn’t the first magazine cover to define the pair’s relationship. In 2005—a year after they first met, on the set of Mr. and Mrs. Smith, and several months after Pitt broke up with his then wife, Jennifer Aniston—Pitt and Jolie memorably played house in Palm Springs for W in a 60-page portfolio titled “Domestic Bliss.” The concept was a collaboration between Pitt and the photographer Steven Klein, making it all the more the surprising—including to Aniston herself—that he and Jolie had yet to even confirm that they were dating. Naturally, the shoot only served to fuel the speculation, which, several months later, the couple eventually confirmed. Revisit the shoot that started it all—including “Brangelina,” the defining portmanteau of the mid-aughts—here.