Pitt and Aniston formally separate. "We would like to explain that our separation is not the result of any of the speculation reported by the tabloid media," they say in a statement. "This decision is the result of much thoughtful consideration."
Pitt and Jolie pose for a steamy W magazine spread featuring them as husband and wife. "The only time Brad and Angelina came in contact with each other was to take a picture," an onlooker tells PEOPLE. Yet "there was definitely that wink-wink feeling on the set."
Pictures of Pitt and Jolie frolicking with her 3-year-old son Maddox on Kenya's Diani Beach give credence to tabloid reports that they are a couple. Despite sharing a $2,000-a-night oceanside villa and journeying on a half-day safari at the Shimba Hills National Reserve, the newly crowned "Brangelina" refuse to confirm their coupledom. In June, Pitt denies that Jolie is a "home wrecker" in an interview with Diane Sawyer.
Pitt and Jolie welcome baby girl Shiloh Nouvel at the small Cottage Medi-Clinic in Swakopmund, a coastal town of some 20,000 in the African nation of Namibia. The new parents celebrate the birth of their first biological child with a $300,000 donation to purchase maternity ward medical equipment for two state hospitals in the nation. "We want to contribute to Namibia and the people who have been so gracious to us at this time," they say in a statement. The donation, says their philanthropic adviser Trevor Neilson, "is a thank-you and a recognition that not all parents are as lucky, that the world needs to do more to help parents who don't have access to a safe place to have their children."
Jolie adopts 3-year-old Pax Thien from an orphanage outside Ho Chi Minh City, Vietnam. Pitt is unable to accompany Jolie due to his filming schedule, but she brings 5-year-old Maddox and 2-year-old Zahara to welcome their new brother. She filed for adoption solo because Vietnamese law makes it difficult for unmarried couples to adopt, but in April, she asks a California court to change her newly adopted son's last name to Jolie-Pitt.
Pitt is named one of PEOPLE's Most Beautiful, headlining the issue's "Beauty Inside & Out" feature on humanitarianism with Jolie. "Being a father means being concerned about the plight of all children," he says, "especially the children who don't have the opportunities mine have." A week later, Pitt is named one of Time's 100 Most Influential People in the World for "showing off his serious side" with producing projects like A Mighty Heart (starring Jolie) and the documentary God Grew Tired of Us.
Three months after breaking ground in New Orleans' Lower Ninth Ward, Pitt returns to see the two-story, 1,400-sq.-ft., environmentally-friendly home he built with Global Green USA and the Home Depot foundation. "Katrina was a man-made disaster. This is a man-made solution," Pitt tells PEOPLE of the home he built for low-income victims of Hurricane Katrina. "I think we'll really improve quality of life. That's what I call a victory."
Adding to their brood (Maddox, Pax, Zahara, and Shiloh), Pitt and Jolie welcome twins, a boy, Knox Léon, and a girl, Vivienne Marcheline in Nice, France. Just hours after cutting the umbilical cords, Pitt tells the mayor of Nice, "I'm the happiest father ever." In August, the proud parents debut their twins on the cover of PEOPLE, where Pitt says, "[It's] still a cuckoo's nest."
With Cate Blanchett, Pitt stars in The Curious Case of Benjamin Button, about a man who ages in reverse. The film rakes in $11.8 million opening day, making it the second-highest Christmas-opening of all-time. "It's a movie in the vein of the classics," says Pitt. "[It's a] classic epic, dealing with life and love, and all that fantastic stuff." His performance earns him Golden Globe, Oscar and SAG nominations for best lead actor.
BIOGRAPHY (top to bottom): Malibu Media; George Pimentel/WireImage; Mark Mainz/Getty; Merrick Morton/Paramount Pictures