They'll play the iconic venue's Nashville Meets London show on July 18, with support from American singer Michael Ray, Canadian singer-songwriter Tenille Townes, and Yorkshire-born country star Twinnie.
With the Royal Albert Hall currently closed for the first time since The Blitz, the At Home series hopes to raise funds to support the venue, and has already featured artists such as Richard Thompson, David Ford and Baxter Dury.
“This series has spotlighted an incredible collection of world class talents working in an extraordinary array of genres," says the Hall's artistic director, Lucy Noble. "We’re absolutely delighted to announce this first country music concert as part of Royal Albert Home, showcasing four fantastic acts who’ll bring a little bit of Nashville into your living room.
"This line-up illustrates just how exciting and eclectic the world of country is right now, and we can’t wait to share the show with you."
The session will be broadcast on the Royal Albert Hall's website at 19.30 BST on July 18.
At the end of last month The Cadillac Three band released a new version of The Jam, originally found on last year's Country Fuzz album. Roughened up around the edges, the revitalised song has been retitled The Jam (+ Fuzz).