Official, if not surprising, word of the uncoupling comes just a day after an interview appeared in Us Weekly in which Jolie confirmed speculation that the two had been living apart for four months and revealed they hadn't seen or spoke to each since June 3.
"I'm angry. I'm sad. It's a very difficult and sad time," the 27-year-old actress told the magazine in the interview released Wednesday. "It was a real deep connection, a deep marriage."
Turns out, Jolie also put their two-year union in the past tense on Wednesday, filing for divorce in Los Angeles Superior Court, citing irreconcilable differences.
The main "irreconcilable difference" in this case seems to involve the couple's newly adopted 11-month-old son.
Last November, Jolie and Thornton visited a Cambodian orphanage, where, the couple announced in March, they "met a little boy we felt a connection to and that we wanted to be our son." The boy, since named Maddox, came to live in his new home in the States in June.
Eleven days later, according to Jolie's court papers, Thornton moved out.
"It's clear to me that our priorities shifted overnight," she explained to Us.
Jolie is asking for sole custody of Maddox, with Thornton granted visitation. She also wants all her jewelry and personal effects, as well as her earnings since their separation. She also is asking the court not to grant spousal support to Thornton (who, aptly enough, recently starred in The Man Who Wasn't There).
"It's a sad thing," the 46-year-old Thornton said via his publicist.
In happier times, Jolie and Thornton put on a good show. There were the complementary tattoos (hers says "Billy Bob," his, "Angelina"). There were the lingering kisses on the red carpet. There were the vials of blood they wore around their necks (hers contains his droplets, his contains hers).
Then there were the interviews. In 2000, Thornton told Us, "I was looking at her sleep, and I had to restrain myself from literally squeezing her to death. Sex for us is almost too much."
For her part, Jolie once said she broke down on a set "screaming about how much I wanted him."
The two met while shooting 1999's Pushing Tin and married in Las Vegas in May 2000. It was her second, his fifth. (He also has two young sons and a daughter from previous unions.)
Their day jobs, however, have kept them increasingly apart. Jolie, an Oscar winner for Girl, Interrupted, has been out of the country in recent months, shooting the drama Beyond Borders and touring refugee camps as a United Nations goodwill ambassador. She'll soon be taking off again to reprise her Lara Croft duties in a sequel to Tomb Raider.
Thornton, himself Oscar'd for writing Sling Blade, has recently been touring with his band, including a few dates opening for Elvis Costello.