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Val Kilmer admitted he was smitten by Angelina Jolie long before they started filming the 2004 movie “Alexander” together.

The 60-year-old opened up about his love life and health battle with throat cancer in a new memoir titled “I’m Your Huckleberry,” which was released on Tuesday.

The actor previously dated Darryl Hannah, Cindy Crawford, Cher and Jolie, among others.

“When people ask me what Angelina is like, I always say she’s like other women and other superstars, but just more,” Kilmer wrote, as reported by Us Weekly.

“More gorgeous,” he continued. “More wise. More tragic. More magic. More grounded. Is it worth it? Worth knowing people who require weeks of effort to understand even a little? Yes.”

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Val Kilmer and Angelina Jolie, circa 2005.

Val Kilmer and Angelina Jolie, circa 2005. (Julien Behal/Getty Images)

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According to the outlet, Kilmer met Jolie, now 44, on a New York street shortly before Oliver Stone cast them as King Philip II and Queen Olympia in the epic drama.

“We developed a friendship,” he explained. “I was around when Angie’s mom [Marcheline Bertrand] was losing her battle with cancer. They were living in her mom’s favorite hotel. Or maybe it was Angie’s. I happened to be staying there myself. It was meaningful and mortal and effortless and exquisite.”

The star shared that he told Stone he would “only do [‘Alexander’] if the king and queen could have flashbacks to falling hard for each other and storming the castle with passion, before turning against each other.”

Kilmer claimed he “was only half kidding” but the Hollywood filmmaker “didn’t pick up on the humor.”

Still, Kilmer was eager to rehearse with Jolie, who had recently separated from her second husband, Billy Bob Thornton.

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Val Kilmer said he 'couldn't wait' to kiss co-star Angelina Jolie.

Val Kilmer said he 'couldn't wait' to kiss co-star Angelina Jolie. (Yui Mok - PA Images/PA Images via Getty Images)

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“I couldn’t wait to kiss Angie, buy her [a] Gulfstream jet and have V+J painted in rainbow glory on the trail,” he wrote. “She had recently adopted her first child, Maddox, and the paparazzi were obsessed with this postmodern Madonna, the perfect picture of unapproachable stardom and impossibly chic maternal instinct.”

But unfortunately for Kilmer, Jolie ended up falling in love with another co-star. It happened to be Brad Pitt while they were filming “Mr. & Mrs. Smith.” Their whirlwind romance was widely rumored to have caused Pitt’s divorce from Jennifer Aniston in 2005.

Jolie and Pitt, 56, dated for nearly a decade before tying the knot in 2014. The parents of Maddox, 18, Pax, 16, Zahara, 15, Shiloh, 13, and twins Knox and Vivienne 11, separated in 2016. The former couple became legally single in 2019.