He played the urbane, profligate gunslinger Doc Holliday in “Tombstone” (1993), a bloody western, alongside Kurt Russell, Sam Elliott and Bill Paxton as Wyatt, Virgil and Morgan Earp. He was part of a robbery gang in “Heat” (1995), a contemporary urban “High Noon”-ish tale that was a vehicle for Robert De Niro as the mastermind of a heist and Al Pacino as the cop who chases him down. He was a co-star, billed beneath Michael Douglas, in “The Ghost and the Darkness” (1996), a period piece about lion hunting set in late 19th century Africa. In “Pollock” (2000), starring Ed Harris as the painter Jackson Pollock, he was a fellow artist, Willem de Kooning. He played Philip of Macedon, the father of Alexander the Great (Colin Farrell), in Oliver Stone’s grandiose epic “Alexander” (2004).
Throughout his career Mr. Kilmer often left an impression, with movie viewers as well as moviemakers, of unpredictability.
“Most actors recognize there’s something different in Val than meets the eye,” Mr. Stone said in a 2007 interview for a segment of the television series “Biography.” David Mamet, the playwright and screenwriter who directed Mr. Kilmer in the political thriller “Spartan” (2004), added, “What Val has as an actor is something that the really, really great actors have, which is they make everything sound like an improvisation.”
On the screen, he was both charismatic and curiosity-piquing, an actor who didn’t let his characters give emotional clues away easily. Off the screen, he had his share of disagreements, especially early in his career, when he earned a reputation for surliness and self-involvement. A 1996 cover article about him in Entertainment Weekly was titled “The Man Hollywood Loves to Hate.”
“He offended people by being hard to understand,” said Mr. Stone, one of several people over the years who said Mr. Kilmer turned them off before turning them back on again. Robert Downey Jr., who co-starred with Mr. Kilmer in the wry 2005 murder mystery “Kiss Kiss Bang Bang,” acknowledged in the “Biography” segment that he couldn’t stand him when they first met, though they eventually became great friends.