In what will surely be remembered as one of the most memorable pairings in the history of 'CMT Crossroads,' Lee Ann Womack will appear with John Legend in an upcoming episode, which will air next month.

"Having John and Lee Ann join us on 'CMT Crossroads' is going to be an incredible pairing -- they are both among the most respected singers in their genres," CMT's Senior Vice President of Music, Events and Talent John Hamlin says. "This has all the makings of another classic 'Crossroads' collaboration."

The songstress is clearly thrilled with the pairing.

"CMT asked me do 'Crossroads' with John Legend... a singer's singer, a man who blurs boundaries," she writes on her Facebook page. "I'm honored -- This is gonna be awesome, and who knows what kind of hybrid we'll create?"

Womack will release her new album, 'The Way I'm Livin,' on Sept. 23 on Sugar Hill Records.

“I wanted songs that talked about how life really is, the raw spots, the tough places, the meltdowns and messy parts,” she explains. “Hard, sad, rough … all the stuff people pretend doesn't exist! Because once you embrace that, you can figure out what to do -- or not do!”

Other recent 'CMT Crossroads' episodes include Lady Antebellum with Stevie Nicks, Dierks Bentley and One Republic, the Band Perry and Fall Out Boy, and Kacey Musgraves with Katy Perry.

The episode is being taped in Franklin, Tenn., and will premiere on Sept. 26 at 10:00 PM ET on CMT.

Pre-order 'The Way I'm Livin' here.