But unlike the big game, both sides are sure to leave happy.
The "CMT Crossroads" concert will be televised live from Grand Prairie, Texas, just outside of Dallas, on CMT Saturday night as part of the Pepsi Super Bowl Fan Jam festivities. The "Crossroads" TV series pairs country music stars with popular artists in other genres, and this is only the second time ever it's been done live.
"I'm crazy, I guess," said Hill in a recent phone interview. "By doing it live, it just brings another whole element to the show."
Pretenders lead singer Chrissie Hynde expects a bit of "chaos," but playing live is what she loves.
"To me, a gig's a gig, and you have to burn through it," she said in a separate phone interview. "If you (mess) it up, then just live with it. ... You don't remember watching a CD, do you?"
Hill and Hynde will do eight songs together, four from each of their repertoires, and they'll share in the singing, exchanging verses and choruses. The catalog of the Pretenders, Rock and Roll Hall of Famers, includes hits like "Brass in Pocket," ''Back on the Chain Gang" and "I'll Stand by You." Hill, a multiplatinum Grammy-winner, has charted 13 No. 1 country singles, including "Wild One," ''Piece of My Heart" and "This Kiss."
Until Thursday, the two had never met in person, but over they phone, they immediately hit it off.
"We had to make ourselves stop talking so we could save some spontaneity for the show," said Hill. "We talked about music for a while, and it just went on to other things."
Hynde said she's excited about working with a country artist - something she's never done - and she thinks their styles will blend nicely. The last Pretenders' album, 2008's "Break Up The Concrete," had a rockabilly flavor to it, and they have a pedal steel guitar player in the band.
The Super Bowl hype itself does nothing for Hynde. She grew up in Akron, Ohio, but she's lived in England for almost 40 years and would rather watch snooker than American football. Hill, on the other hand, has been NBC's voice for Sunday Night Football for the past three years and has sung "America The Beautiful" and the national anthem at past Super Bowls. She knows what to expect from Saturday night's crowd.
"There's no other time that you have this type of energy in a city," said Hill. "There's such a level of excitement and anticipation and an element of celebration and whenever you have those things in the same place, you want to hear music. You want to go to parties. There's festivities all the time."
The Pittsburgh Steelers play the Green Bay Packers in Super Bowl XLV on Sunday.