Gwyneth Paltrow and Brad Pitt ... their engagement lasted six months.

At the time of his Thelma & Louise breakthrough in 1991, Pitt was dating teen actor Juliette Lewis. A year after their three-year partnership ended, Pitt told Vanity Fair he still loved Lewis: “The problem is, we grow up with this vision that love conquers all and that’s just not so, is it?”

Brad Pitt and Juliette Lewis during The Last of the Mohicans Los Angeles Premiere.Source:Supplied

For 2 ½ years, Pitt was then with Gwyneth Paltrow; the pair got engaged in December 1996. But six months later it was over.

Paltrow later blamed herself, admitting she was “a mess” at the time.

Then came Jen: Pitt and Friends star Jennifer Aniston were reportedly set up on a blind date in 1999. They were married in July 2000 and were Hollywood’s ‘It’ couple until Brad met Angelina on the set of Mr & Mrs Smith.

Brad Pitt and Jennifer Aniston at the 56th Annual Primetime Emmy Awards in 2004.Source:Supplied

Both have denied there was any cheating before Pitt and Aniston officially split in 2005, Pitt saying there was no “dastardly affair ... it was respectful” and Jolie telling Vogue that she was aware Pitt was with “his best friend” and that she herself was “content to be a single mum”.

“It took until the end of the shoot for us to realise that it might mean something more than we’d earlier allowed ourselves to believe,” Jolie said.

Jolie was, at the time, considered dark and weird — a Hollywood wild child.

Actor Billy Bob Thornton with wife Angelina Jolie at the premiere of the film Gone in 60 Seconds in 2000.Source:Getty Images

She’d been married from 2000 to 2003 to actor Billy Bob Thornton, 20 years her senior.

Their relationship remains infamous for the vials of blood each wore around their necks during their time together.

Thornton told the Hollywood Reporter the vials were Jolie’s idea: “She thought it would be interesting and romantic if we took a little razor blade and sliced our fingers, smeared a little blood on these lockets and you wear it around your neck.”

From that, he added, the public perception of the weirdness of their union was greatly exaggerated: “We were wearing quart jars of blood around our necks and we were vampires and we lived in a dungeon.”

Though they announced the adoption of Jolie’s first child Maddox together, Jolie and Thornton were done just three months later.

Thornton has said there was no hate: “I chickened out because I didn’t feel good enough.”

Angelina Jolie and Jonny Lee Miller at the Beverly Hilton Hotel in Beverly Hills, California, in 1998.Source:Getty Images

Jolie had already been married once before — to English actor Jonny Lee Miller. They met on 1995 movie Hackers.

Angelina Jolie and Jonny Lee Miller in the 1995 film Hackers.Source:Supplied

Jolie famously wore black rubber pants and a white T-shirt with Miller’s name scrawled on it in blood to their intimate 1996 ceremony.

When asked why by the New York Times, she replied: “It’s your husband. You’re about to marry him. You can sacrifice a little to make it really special.”

Jolie and Elementary star Miller divorced in 1999, but have always remained on good terms.

There was one more that got away for Jolie — this one a woman.

Jolie met model and actor Jenny Shimizu on 1996 movie Foxfire and a year later told lesbian magazine Girlfriends: “I probably would have married Jenny Shimizu if I hadn’t married my husband (Miller). I fell in love with her the first second I saw her.”

Jenny Shimizu and Angelina Jolie in the 1996 movie Foxfire.Source:Picture Media

She added Miller was well aware of her feelings for Shimizu.

“He was around when I was realising that I was attracted to women also ... He didn’t treat it just like some sexy thing.”

Oddly enough, in that same 1997 Girlfriends interview, Jolie was asked what she thought about Miller being “described as Britain’s Brad Pitt”.

Jolie laughed and replied: “I don’t know Brad Pitt.”