In 2009, Hetfield was ranked at no. 8 in Joel McIver's book The 100 Greatest Metal Guitarists, and ranked at no. 24 by Hit Parader on their list of the 100 Greatest Metal Vocalists of All Time. In Guitar World's poll, Hetfield was placed as the 19th greatest guitarist of all time, as well as being placed second (along with Metallica lead guitarist Kirk Hammett) in The 100 Greatest Metal Guitarists poll of the same magazine. Rolling Stone placed Hetfield as the 87th greatest guitarist of all time.
- Hetfield sang "Stone Cold Crazy" at the Freddie Mercury Tribute Concert, accompanied by the remaining members of Queen and Tony Iommi on rhythm guitar.
He provided backing vocals on "Man or Ash" on the Corrosion of Conformity album Wiseblood.
He sang backing vocals on "Twist of Cain" and "Possession" on Danzig's debut album, Danzig.
He played guitar on "Eclectic Electric" from the Primus album Antipop.
Though previously believed to have been sung by Trey Parker, the song "Hell Isn't Good" from the film South Park: Bigger, Longer and Uncut was actually sung by Hetfield. He admitted to doing so in 2000, confirming what many Hetfield fans had already recognized as his trademark growling style.The Playboy Interview: Metallica (April 2001).
Hetfield sang on the Gov't Mule song "Drivin' Rain" with fellow guest Les Claypool, which appears on the compilation album Crank It Up with NASCAR.
He also performed at the Outlaws Concert in 2004, alongside Hank Williams Jr., Cowboy Troy, Big & Rich, Gretchen Wilson, and Kid Rock. Hetfield played one of close friend Waylon Jennings's songs, "Don't You Think This Outlaw Bit's Done Got Out of Hand," the very same he recorded on the tribute album to Jennings, I've Always Been Crazy. At this same event, he performed Metallica's "Mama Said" with Jesse Colter, the widow of Waylon Jennings, though this was cut from the television broadcast.
Hetfield, as well as Metallica's lead guitarist Kirk Hammett, voiced characters in a number of episodes of the Adult Swim cartoon Metalocalypse.
He also appeared as a guest in an episode of Space Ghost Coast to Coast entitled "Jacksonville" alongside Hammett.
Hetfield, along with the current Metallica lineup, appeared on an episode of Discovery's Time Warp, aptly titled "Metallica."
Hetfield appeared on an episode the MTV show, Celebrity Deathmatch in which he killed Limp Bizkit vocalist, Fred Durst, but he and ref Mills Lane disappeared after Mankind jumped from the top of the roof and onto the ring and then it collapsed.
A photo of Hetfield appeared on Rammstein's music video Haifisch, and was apparently "picked" to be the replacement for the "dead" Till Lindemann (only a video set and was not official despite him actually still alive as seen later in the clip).
Hetfield and Metallica also appeared in a Simpson's episode, "The Mook, the Chef, the Wife and Her Homer".
Hetfield appeared onstage with Seattle grunge band Alice in Chains in 2006 at Rock Am Ring, singing deceased lead vocalist Layne Staley's vocal parts on the song "Would?". Alice in Chains guitarist Jerry Cantrell has also joined Metallica in concert, performing "Nothing Else Matters".
Hetfield and filmmaker Justin Hunt were interviewed about the documentary Absent, which was directed by Hunt and features Hetfield and takes a look at the effects of absent fathers on their children, on Fox News Channel's Fox and Friends program on March 30, 2011.
Hetfield is a playable character in Tony Hawk's Pro Skater HD.
Hetfield appeared on the 2012 CMT Artists of the Year Awards Show to congratulate his friend, Eric Church on being named one of the Artists of the Year.
On November 17, 2000, James Hetfield was at a Misfits concert accompanied by his body guard at Maritime Hall in San Francisco, where he eventually got up on the stage and sang "Last Caress", then "Die, Die My Darling" whilst being accompanied by the band.
On February 1, 2016, James Hetfield appeared in the American Dad! episode The Life Aquatic with Steve Smith as a water polo coach, constantly denying that he was The James Hetfield.
James performed guest vocals on the Heart song "Beautiful Broken" from their album of the same name which was released on July 8, 2016.