The stars will take the stage at the annual Pepsi Super Bowl Fan Jam on the night before the Super Bowl is held in Indianapolis, Indiana.
Tyler and Underwood previously performed a duet at the 2011 Academy of Country Music Awards, which drew rave reviews from viewers and critics.
The televised special will mark the second year Crossroads has aired from the Super Bowl, following last year's pairing of Faith Hill and The Pretenders.
CMT Crossroads: Steven Tyler & Carrie Underwood Live From the Pepsi Super Bowl Fan Jam is broadcast on February 4 on CMT.
It was recently announced that Kelly Clarkson will sing the National Anthem to kick off the Super Bowl on February 5.
Madonna will star in Super Bowl XLVI's half-time show.
> Kim Kardashian wasn't replaced in Skechers Super Bowl ad, says CEO
> Bret Michaels, LMFAO for Super Bowl week concerts
Watch Carrie Underwood and Steven Tyler perform at the Academy of Country Music Awards below: