The song will be heard when Cullen Bohannon, played by Anson Mount, and Louise Ellison, played by Jennifer Ferrin, dance a Texas two-step together at a saloon.
AMC said Daniels signed on for the assignment after striking up a Twitter friendship with Mount and telling him he is a fan of the 19th century-set western series.
"I sent him a complimentary tweet saying how much I enjoyed the show and we started going back and forth a little and then he asked me if I'd be willing to write a song for the show," Daniels said in a statement. "It's about my favorite television show right now, so I said, 'Sure, what do you want?'"
"In the world of country music, Charlie Daniels is one of the grand royalty," said Mount. "It's a hell of a track and works great for the scene, and I'm touched and thrilled that Charlie would do this for us and that he's a fan of the show."