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Carrie and Tony first teamed up last year, when they cut a version of 'It Had to Be You' for the crooner's 'Duets II' album.
"I would have sang anything with Tony! Whatever he wanted, I was there," Carrie tells PBS, explaining how psyched she was to partner with the 'I Left My Heart in San Francisco' singer. "He wants to do duets with people as themselves and have them bring their thing and him bring his thing, and I respect that so much, his way of recording."
Carrie is the latest in a string of country artists who have signed on for the 54th Grammy Awards, which will broadcast live from the Staples Center in Los Angeles.
Others include Jason Aldean, who's set to sing with his 'Don't You Wanna Stay' duet partner Kelly Clarkson; the iconic Glenn Campbell, who will join forces with the Band Perry and Blake Shelton; and of course, America's sweetheart, Taylor Swift.
Dierks Bentley and Miranda Lambert will also be on hand, though they'll be presenting gramophone statuettes rather than strumming their guitars.
The 54th Annual Grammy Awards air live from the Staples Center at 8PM EST on Feb. 12, 2012.