Pitt was married to Jennifer Aniston and Jolie had recently filed for divorce from Billy Bob Thornton at the time of filming around 2003.

People reported that in a 2006 interview, Jolie confirmed to Vogue that they began developing feelings for each other. She said, "I think we found this strange friendship and partnership that kind of just suddenly happened. I think a few months in I realized, 'God, I can't wait to get to work.'"

She added: "It took until, really, the end of the shoot for us, I think, to realize 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 months of rumors that Pitt and Jolie had an affair on the set of "Mr. & Mrs. Smith," Pitt and Aniston released a statement about their separation to People: "For those who follow these sorts of things, we would like to explain that our separation is not the result of any of the speculation reported by the tabloid media."

Shortly after the announcement, People reported that Aniston filed for divorce, citing "irreconcilable differences."

A month later, Us Weekly published photos of Pitt and Jolie with Jolie's son, Maddox, in Kenya. 

In September 2005, Aniston told Vanity Fair: "The world was shocked, and I was shocked."

The now-iconic spread included many photos of the two as a couple with a family. 

That same month, People reported that Jolie adopted 6-month-old Zahara from Ethiopia with Pitt by her side.

Less than a year after Pitt's divorce from Aniston was finalized, People confirmed Jolie and Pitt were expecting a child.

That same month, a judge granted a request to change Maddox and Zahara's last names to Jolie-Pitt.

In May, Shiloh Jolie-Pitt was born in Namibia. Their obstetrician told People that Pitt was in the operating room the whole time.

In March, Pax, 3, became the newest member of the Jolie-Pitt family, after the couple traveled to Vietnam to adopt him.

Reuters reported that Jolie supposedly filed the papers without Pitt because Vietnamese law does not allow unmarried couples to adopt children, but single individuals can. 

Jolie announced she was expecting twins at the 2008 Cannes Film Festival,

She told Access Hollywood, "We weren't expecting twins. So it did shock us."

Knox Leon and Vivienne Marcheline were born in Nice, France in July.

A month later, they appeared on the cover of People. Jolie talked about their family life in an interview with the magazine, saying, "It is chaos, but we are managing it and having a wonderful time."

In February 2010, News of the World reported the couple had split. The couple later sued the publication for the false report.

In July, BBC News reported that the couple was paid damages from the company that owns the newspaper and planned to donate it to their charity, the Jolie-Pitt foundation. 

Pitt's manager confirmed to People that the couple was engaged, saying: "It is a promise for the future and their kids are very happy. There's no date set at this time." 

Jolie wrote a New York Times op-ed about undergoing the surgery, writing: "I am fortunate to have a partner, Brad Pitt, who is so loving and supportive … Brad was at the Pink Lotus Breast Center, where I was treated, for every minute of the surgeries."

She added: "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."

Pitt and Jolie privately wed at their Chateau Miraval in France and all of their six children were involved in the ceremony.

Maddox and Pax walked their mom down the aisle, Zahara and Vivienne were flower girls, and Shiloh and Knox were ring bearers. Jolie wore an Atelier Versace gown and a veil that featured designs from her kids' drawings embroidered into the fabric.

Pitt and Jolie starred in their second film together, a relationship drama called "By The Sea" which Jolie directed.

After an annual blood test showed markers that could be "a sign of early cancer," Jolie decided to have her ovaries and fallopian tubes removed as a preventative measure.

One of the last times Pitt and Jolie were publicly spotted together as a couple was in July 2016, when they were photographed with Shiloh.

Prior to this, they had been apart for months while working on various projects.

Citing irreconcilable differences, Jolie officially filed for divorce. She petitioned for primary custody of the six children.

In September, during a family flight on the couple's private jet, Pitt was reportedly "drinking heavily." Early reports alleged that Pitt physically hurt 15-year-old Maddox Pitt-Jolie during the flight, but later reports stated that Jolie separated Pitt from their kids.

Pitt was later investigated by The LA Department of Children and Family Services and the FBI, but both cleared Pitt of all charges in November.

The couple then hired a private judge and reportedly signed agreements to keep the details of their case private. After that, they were relatively quiet about their split for a while. 

Jolie's attorneys said in a court filing that Pitt hadn't paid any "meaningful" child support since they split. It was not clear at the time of the filing what constituted "meaningful" support.  

Pitt's lawyers said in return that Pitt had in fact paid Jolie more than $1.3 million in contributions over the past two years and that Pitt gave Jolie an $8 million loan to buy a new property. Her camp denied that he was meeting his legal obligations for child support. Pitt's attorneys also accused Jolie via court filing of trying to "manipulate media coverage" of their divorce. 

Though their divorce was still in progress, Judge John W. Ouderkirk entered a judgment saying the couple was no longer married. Her name was also restored to Jolie, not Jolie Pitt.

Business Insider reported that the private judge hired by both stars awarded Pitt more custody of his children following months of witness testimony.

"Pitt has always been seeking the opportunity to have more time with his children and prioritized their well being while the other side did everything to try and stop that," a source familiar with the situation told BI in May 2021.

Pitt and Jolie purchased a controlling stake in Château Miraval and its vineyard behind the popular wine in 2008. The two were also married on the estate in 2014. 

According to court documents, lawyers for Pitt say Jolie sold her stake in the Château to the Russian oligarch Yuri Shefler without her ex-husband's knowledge.

"She sold her interest with the knowledge and intention that Shefler and his affiliates would seek to control the business to which Pitt had devoted himself and to undermine Pitt's investment in Miraval," the lawsuit claimed.

The lawsuit continued to state that Jolie's sale was intended to cause Pitt "gratuitous harm" after he had "poured money and sweat equity" into the business. Pitt's lawyers also said that the pair had previously agreed to never sell their respective financial interests in the Château without the other's consent.

According to a leaked FBI report obtained by Rolling Stone and Puck, Jolie alleged in an interview with the FBI that Pitt "grabbed her by her head," shook her, "pushed her into the bathroom wall," and repeatedly punched the ceiling of the private plane during an "outburst" about 90 minutes into a flight from Paris to Los Angeles on September 14, 2016.

The report added that Jolie alleged Pitt was intoxicated during the flight, saying that he poured beer on her at one point. Jolie told the FBI that by the time the plane landed, there was $25,000 worth of damage from Pitt spilling red wine, Rolling Stone reported.

Rolling Stone reported that Jolie alleged her children were scared at the time of the incident. She told the FBI that one child called Pitt a "prick," prompting him to lunge at the kid, only to be stopped when Jolie grabbed him from behind "like in a choke hold."

As previously mentioned, BI reported in 2016 that the FBI cleared Pitt of child abuse allegations regarding that incident.

Jolie and Pitt signed off on their divorce on December 30, 2024, People reported.

No details of the divorce settlement were revealed.

"More than eight years ago, Angelina filed for divorce from Mr. Pitt. She and the children left all of the properties they had shared with Mr. Pitt, and since that time she has focused on finding peace and healing for their family," Jolie's lawyer James Simon told BI in a statement. "This is just one part of a long ongoing process that started eight years ago. Frankly, Angelina is exhausted, but she is relieved this one part is over." 

Pitt's representative declined to comment when contacted by BI.