The Star Trek legend will take to the stage at Chicago's Douglass Park on September 20, and said of the honour in a statement: "I've always believed that music, like space, is about exploration.
"Riot Fest is exactly the kind of place where anything can happen. We're bringing volume, intensity, and a few surprises. I can't wait to share this experience with the fans."
Shatner also shared his excitement on his Instagram page, telling fans: "This is an event you definitely will be telling your grandchildren about!"
Meanwhile, Riot Fest founder Mike "Riot Mike" Petryshyn quipped that he had been trying for years to get the 95-year-old to his festival.
He said: "After years of persistently - and perhaps annoyingly - writing letters to William Shatner about performing at Riot Fest, it appears that he was finally compelled.
"I for one cannot wait to see Shatner get heavy."
The *uckers features Marcus Nand on guitar, Fred Aching on drums, Britt Lightning on guitar and Phil Soussan on bass.
According to People, the performance will "reimagine songs" from Shatner's back catalogue, as well as debuting tracks from The *uckers' heavy metal album What the F Is Heavy Metal.
Shatner told People: "That's the name of the album because I know nothing or didn't know anything until I found out how little I do know!"
Other performers to take to the stage at Riot Fest this year include Morrissey, Iggy Pop, Sex Pistols, Was, Twenty One Pilots and Patti Smith.
Shatner Riot Fest debut comes after he made history when he became the oldest person to go up into space when he blasted off on Jeff Bezos' New Shepard NS-18 rocket in October 2021.
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