Val Kilmer, a homegrown Hollywood actor who tasted leading-man stardom as Jim Morrison and Batman, but whose protean gifts and elusive personality also made him a high-profile supporting player, died on Tuesday in Los Angeles. He was 65.

The cause was pneumonia, said his daughter, Mercedes Kilmer. Mr. Kilmer was diagnosed with throat cancer in 2014 but later recovered, she said.

Tall and handsome in a rock-star sort of way, Mr. Kilmer was in fact cast as a rocker a handful of times early in his career, when he seemed destined for blockbuster success. He made his feature debut in the slapstick Cold War spy-movie spoof “Top Secret!” (1984), in which he starred as a crowd-pleasing, hip-shaking American singer in Berlin unwittingly involved in an East German plot to reunify the country.

He gave a vividly stylized performance as Jim Morrison, the frontman for the rock group the Doors and an emblem of psychedelic sensuality, in Oliver Stone’s “The Doors” (1991), and he played the cameo role of Mentor — an advice-giving Elvis as imagined by the film’s antiheroic protagonist, played by Christian Slater — in “True Romance” (1993), a violent drug-chase caper written by Quentin Tarantino and directed by Tony Scott.

Mr. Kilmer had top billing, ahead of Sam Shepard, in “Thunderheart” (1992), in which he played an unseasoned F.B.I. agent investigating a murder on a South Dakota Indian reservation, and in “The Saint” (1997), a thriller about a debonair, resourceful thief playing cat-and-mouse with the Russian mob. Most famously, perhaps, between Michael Keaton and George Clooney, he inhabited the title role (and the batsuit) in “Batman Forever” (1995), doing battle in Gotham City with Two-Face (Tommy Lee Jones) and the Riddler (Jim Carrey), though neither Mr. Kilmer nor the film was viewed as stellar representatives of the Batman franchise.

“Serious audiences will be less interested than ever in what’s under Batman’s cape or cowl,” Janet Maslin wrote in The New York Times. “There’s not much to contemplate here beyond the spectacle of gimmicky props and the kitsch of good actors (all of whom have lately done better work elsewhere) dressed for a red-hot Halloween.”

But by then another, perhaps more interesting, strain of Mr. Kilmer’s career had developed. Mr. Scott cast him in his first big-budget film, “Top Gun” (1986), the testosterone-fueled adventure drama about Navy fighter pilots in training, in which Mr. Kilmer played the cool, cocky rival to the film’s star, Tom Cruise. It was a role that set a precedent for several of Mr. Kilmer’s other prominent appearances as a co-star or a member of a starry ensemble. (He reprised it in a brief cameo in the film’s 2022 sequel, “Top Gun: Maverick,” also starring Mr. Cruise.)

Mr. Kilmer 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. And 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.