In an interview with the Boston Globe, Jolie explains why she and Thornton wear vials of each other's blood around their necks. "Some people think a big diamond is really pretty," she says. "My husband's blood is the most beautiful thing in the world to me." The couple also sign their wills in blood the same year, and for a first-anniversary present, Jolie buys Thornton his-and-hers cemetery plots in his native Louisiana.
While researching her role as a socialite turned philanthropist in Beyond Borders, Jolie embarks on two goodwill trips for the United Nations High Commissioner for Refugees. After meeting war victims in Sierra Leone, Jolie tells PEOPLE, "My impressions are hard to cope with, so I write them down." In 2003 her journals are published as Notes From My Travels. In August, she is appointed goodwill ambassador for the UNHCR.
It comes as a surprise when the once-reckless Jolie adopts a baby boy from Cambodia, the country she fell in love with while filming Lara Croft: Tomb Raider. She names him Maddox, and only puts her name on the adoption papers, a move that implies a rift in her marriage with Thornton. The pair divorce in May 2003.
Through tears and sobs, her father pleads with Jolie on Access Hollywood to get help for her "serious mental problems." It is the start of a years-long estrangement. Her mother comes to her defense, telling PEOPLE, "There's nothing wrong with Angelina's mental health. Mentally and physically, she is magnificently healthy." Jolie says, "It's horrible."
Jolie travels to Thailand to have a Buddhist prayer of protection for her son Maddox tattooed onto her left shoulder blade. The Thai artist uses the traditional method of a hammer and "a foot-and-a-half-long needle," Jolie says to PEOPLE.
Jolie begins filming Mr. & Mrs. Smith with future flame Brad Pitt, and the tabloid rumors that the two are sharing an on-set romance begin. Both Pitt and Jolie deny anything happened. Jolie tells PEOPLE, "If I'm sleeping with somebody, I'm not shy about it."
Partly to impress her son Maddox, Jolie earns her pilot's license. "Every time Mad sees a plane, he's amazed," Jolie says to PEOPLE. "If I could actually fly a plane by the time he's 4, I'll be like Superman to him."
Jolie and Pitt play husband and wife in W magazine – a concept of Pitt's. It hits newsstands after Pitt's separation from Jennifer Aniston and amid romance reports regarding Jolie. A month later, Pitt and her son Maddox are spotted together in Kenya. "The man that enters my home with me and my son – I take that very, very seriously," Jolie tells W.
Pitt accompanies Jolie and Maddox on tours of orphanages in Addis Ababa and Ethiopia, where Jolie finds her second child, daughter Zahara Marley. Jolie is the only parent named on the paperwork, which is finalized July 6. Later that year she tells PEOPLE why adoption means so much to her. "There's something about making a choice," she says, "waking up and traveling somewhere and finding your family."
Jolie and Pitt tour Pakistan, where 73,000 people were killed and more than 3 million left homeless after a massive earthquake.
BIOGRAPHY (top to bottom): Kevin Winter/Getty; Eric Charbonneau/Beimages; L. Taylor/UNHCR; Bauer-Griffin; Access Hollywood; AP; Daniel Mayer; LDP Images; RF/007/Malibu Media; INF; J. Redden/UNHCR