Johnny Lee Miller, 1996

Before she became Mrs. Smith (or Mrs. Pitt) and Lara Croft, Jolie starred in a 1995 gem of a thriller, Hackers. The tech crime, one of the first, would cement her in pop culture and introduce her to her first husband, Elementary‘s Johnny Lee Miller, who was fresh off a starring role in Trainspotting.

Six months later, the young up-and-comers said their I do’s, in March of 1996, in a small civil ceremony in front of her mother and one of his friends. And the bride wore…black rubber? True to Angelina Jolie fashion, the actress donned a pair of black rubber pants and a T-shirt with Johnny Lee Miller’s name written on it in her own blood. “It’s your husband. You’re about to marry him,” she told The New York Times. “You can sacrifice a little to make it really special.” They separated in September 1997 and made their divorce official in February 1999, though the couple still remain friends today.

Billy Bob Thornton, 2000

It’s a tale as old as time: Boy meets girl on movie set, boy and girl marry in jeans at a Vegas chapel, girl wears vial of boy’s blood around her neck. Coming off career-turning roles in Gia and Girl Interrupted, Jolie met her second husband, Billy Bob Thornton (who was engaged to Laura Dern at the time), on the set of 1999’s* Pushing Tin*, where she played his wife.

Two months later, on May 5, 2000, the couple made it official and eloped to Las Vegas’s Little Church of the West Wedding Chapel. Dressed in slouchy jeans, a gray tank top, and boots, Jolie definitely broke with tradition for her second walk down the aisle, and you can’t deny her bridal glow—but, you know, good genes work too. The couple reportedly bought the “Beginning Package” wedding ceremony, and she walked down the aisle to the classic “Here Comes the Bride” while carrying a bouquet of roses and carnations.

“Personally I don’t think they had really planned it out for long, I think it was a spur of the moment deal, but I’m not sure, I didn’t ask, ‘Oh what made you decide to get married?’ It was my job to marry them,” Reverend Jim Hamilton, who married the couple in 2000, told the Daily Mail.

Wearing vials of each other’s blood around their necks wouldn’t keep this Hollywood couple together, and the duo would split in June 2002, after Angelina adopted her first son, Maddox.

“It took me by surprise too, because overnight, we totally changed,” the actress told Vogue in 2004. “I think one day we had just nothing in common. And it’s scary but…I think it can happen when you get involved and you don’t know yourself yet.”

Brad Pitt, 2014

Nine years and six adorable kids later, Mr. and Mrs. Smith finally became Mr. and Mrs. Pitt at an intimate family ceremony in August of 2014. But the couple had already made it official before swapping their I do’s in front of 22 family members, including their children, Maddox, Pax, Zahara, Shiloh, Vivienne, and Knox.

“Before the wedding in France with the kids, Brad and I were already married in California,” Jolie told Italian magazine Io Donna. “As Americans, we couldn’t marry legally in France.”

The ceremony took place at the couple’s French chateau, with the kids playing integral parts in their parents’ big day, from walking their mother down the aisle and carrying the rings to helping design her wedding dress. The bride’s clean, simple white silk-satin Luigi Massi for Versace wedding dress featured a little something extra on the back: dozens of drawings created by her six children sewn into the train and veil. “Luigi is like family to me and I couldn’t imagine anyone else making this dress,” the actress told People. “He knows and cares for the children and it was great fun putting it together.” Talk about a family affair!

For jewelry, the actress kept it close to her heart, wearing a locket that belonged to her mother. The wedding rings were designed by Pitt’s friend Robert Procop, who also created Jolie’s gorgeous 16-carat emerald-cut engagement ring.

So, was third time the charm for Mrs. Jolie-Pitt? “It feels nice to be husband and wife,” she told Vanity Fair later that year.