His daughter Mercedes told the Associated Press he died of pneumonia on Tuesday night in Los Angeles surrounded by family and friends.
Kilmer was diagnosed with throat cancer in 2014 but later recovered, she said.
The actor, who played Tom ‘Iceman’ Kazansky in Top Gun alongside Tom Cruise in 1986, previously admitted he didn’t want the role, which made him famous.
But he said he begged to be part of the sequel, Top Gun: Maverick in 2022, even going as far as contacting the producers and creating “heartrending scenes with Iceman”. It would be his final acting role.
Kilmer had a colourful romantic past, having dated Hollywood stars including Cindy Crawford, Angelina Jolie, Carly Simon and Cher.
He starred in Willow in 1988 and married his British co-star Joanne Whalley. The couple had two children before they divorced in 1996.
As well as his roles in Top Gun, Batman Forever and The Doors, he starred in True Romance, Heat and Kiss Kiss Bang Bang.
He was one of the best-paid actors in the 1990s and in 1992 film critic Roger Ebert wrote, “if there is an award for the most unsung leading man of his generation, Kilmer should get it”.
In 2020 he published a memoir titled I’m Your Huckleberry: A Memoir.
Actor Josh Brolin wrote: “See ya, pal. I’m going to miss you. You were a smart, challenging, brave, uber-creative firecracker. There’s not a lot left of those.
“I hope to see you up there in the heavens when I eventually get there. Until then, amazing memories, lovely thoughts.”
In an Instagram post actor Josh Gad called Kilmer “an icon”.
He said: “RIP Val Kilmer. Thank you for defining so many of the movies of my childhood. You truly were an icon.”
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