"It’s hard to imagine topping what we have accomplished together," she said of her 12 years in the role.
The event, hosted by Carrie Underwood, Reba McEntire and Dolly Parton, saw Garth Brooks win the showpiece Entertainer of the Year award.
The Mercury Nashville release is the latest single by the platinum-selling act.
“He was an extraordinary human being whose generosity, spirituality and humour inspired everyone around him.”
A tribute to the famed Nashville institution that's as old as what we call country music itself.
The song is a contemporary take on the traditional Nashville barroom ballad, with powerful lead and harmony vocals, lead guitar and pedal steel.
The CMAs will be broadcast on ABC from Nashville’s Bridgestone Arena on 13 November.
Running from 3 September to 31 October, it will feature two dozen of the country superstar's wardrobe items, worn on the Opry and at the Ryman Auditorium.
Underwood has co-hosted with Brad Paisley every year since 2008, but will now be joined by McEntire and Parton, as the CMA celebrates legendary female figures of country.
Country duo Maddie & Tae have unveiled the official video for their powerful love song, ‘Die From a Broken Heart’, off their 'One Heart to Another' EP.
A new documentary, Alan Jackson: Small Town Southern Man features interviews with such fellow stars as Carrie Underwood, Alison Krauss and Lee Ann Womack.
Other victors at the Nashville event included Kane Brown, the Zac Brown Band and Ashley McBryde.
This year's event takes place at Nashville's Bridgestone Arena on 5 June.
The country superstar has also launched a contest inviting fans to win the chance to perform the rap from 'The Champion' on the tour.
The five-track release will include both their recent track 'Die From A Broken Heart' and the new 'Tourist In This Town.'