This reggae-flavored track features the Rolling Stones' Keith Richards on guitar. Crow and the Stones go back a long way. She has performed with the British rock group in concert, sung duets with Mick Jagger, and Richards previously appeared on Crow's 1999 Sheryl Crow and Friends: Live from Central Park set. When she came up with this track, there was only one guitarist she could imagine adding his signature slashing riffs to the mix, and Richards duly obliged. "He has been such a champion for me, and the Stones gave me so many breaks along the way, from very early on," she said.
Crow told Rolling Stone that Richards' contribution was not the only way the Stones helped her with the making of 100 Miles From Memphis. "Writing the lyrics, it was like having a term paper hanging over my head," Crow explained. "But I saw the documentary of making Exile on Main St., and there's a scene where Mick has all these tunes that don't have any lyrics, and it made me feel so much better. That's one of my favorite records of all time, and I figure, 'Well, if he had a suitcase full of songs he had to write lyrics for and it turned out that good, there's some hope here.'"
Angus Young created the distinctive opening guitar part for "Thuderstruck" by playing with all the strings taped up, except the B. He learned the studio trick from his older brother George Young, who was the rhythm guitarist for The Easybeats.