Brad and Angelina met on the set of action film Mr and Mrs Smith when Brad was still married to Jennifer Aniston.
According to a report by PEOPLE, Angelina said that she thought they found "a strange friendship and partnership that kind of just suddenly happened."
"I think a few months in I realised, ‘God, I can’t wait to get to work.’ … Anything we had to do with each other, we just found a lot of joy in it together and a lot of real teamwork. We just became kind of a pair,” she explained.
Though a relationship was the last thing either of them were looking for, by the time filming had wrapped, both parties realised there was something there.
“It took until, really, the end of the shoot for us, I think, to realise that it might mean something more than we’d earlier allowed ourselves to believe. And both knowing that the reality of that was a big thing, something that was going to take a lot of serious consideration.”
After five years of marriage, Brad and Jennifer announced that they were separating in 2005. Two months later in March, Jennifer filed for divorce, citing "irreconcilable differences."
But the drama was cranked up a notch when after a holiday in Kenya, Brad and Angelina were featured in an extensive W magazine spread titled Domestic Bliss. Angelina also adopted her daughter Zahara from Ethiopia the same month, accompanied by Brad.
In an interview with Vanity Fair, Jennifer reacted to the photos saying: "The world was shocked, and I was shocked."
Less than a year after Brad and Jennifer's divorce was finalised in 2006, PEOPLE confirmed that Angelina was pregnant with her and Brad's child.
Shiloh Jolie-Pitt was born in Namibia in 2006. But despite chatter of a wedding, Brad stated that he and Angelina wouldn't tie the knot until "everyone else in the country who wants to be married is legally able."
The couple then adopted three-year-old Pax a year later and then another year after that, they welcomed their twins Knox and Vivienne, who wore born in Nice, France.
The first rumour that Brad and Angelina had broken up reared its head in 2010 thanks to a report by News of the World, but the couple sued the publication for the false report and won.
By 2012, it was revealed that Brad and Angelina were engaged and bride-to-be Angelina was spotted wearing a ring estimated to cost one million dollars.
Brad's manager confirmed the couple's happy news saying: "Yes, it's confirmed. It is a promise for the future and their kids are very happy. There's no date set at this time."
But before they could make things official, Angelina revealed in 2013 that she underwent a preventative double masectomy and had her "loving and supportive" partner by her side.
"Brad was at the Pink Lotus Breast Center, where I was treated, for every minute of the surgeries. We managed to find moments to laugh together. We knew this was the right thing to do for our family and that it would bring us closer. And it has," she wrote in a New York Times op-ed.
In August 2014, Brad and Angelina became husband and wife in a private ceremony at their Chateau Miraval in France. All six of their six children were involved in the ceremony - whilst Maddox and Pax walked Angelina down the aisle, Zahara and Vivienne were flower girls, and Shiloh and Knox were ring bearers.
In a sweet move, Angelian's Atelier Versace wedding gown and veil also featured designs from her kids' drawings embroidered into the fabric.
Later that year, the couple worked on their first joint on-screen acting project since Mr and Mrs Smith, the film By The Sea, which was written and directed by Angelina herself.
2015 was one of the last times Angelina spoke about her relationship with Brad before their divorce.
In a second New York Times op-ed, the actress and humanitarian revealed that she elected to have her ovaries and fallopian tubes removed as a preventative measure.
"I called my husband in France, who was on a plane within hours," she wrote.
But a year later, news broke that Angelina had filed for divorce, citing "irreconcilable differences", with the couple's lawyer saying in a statement: "This decision was made for the health of the family. She will not be commenting, and asks that the family be given its privacy at this time."
The divorce led to a bitter custody battle and took its toll on Brad, who admitted his drinking led to troubles at home. However, after spending time in a men’s Alcoholics Anonymous group and focusing on himself and the kids, Brad appears to be on the road to recovery.
After years of tension, a report by Us Weekly revealed that now things between the former couple are "better than they have been".
“They’re more cordial—they’re aiming toward resolutions that work for each of them.”