The Shakespeare In Love star will sing the title track of her new movie Country Strong and will be joined by Vince Gill.
Kenny Chesney, Lady Antebellum, Taylor Swift and Keith Urban are also set to perform at the ceremony, which takes place at Nashville's Bridgestone Arena on 10 November.
Paltrow, 39, has also landed a guest role in the TV musical comedy Glee.
The actress, who is married to Coldplay frontman Chris Martin, will play a supply teacher who falls for high school choir leader Will Schuester.
It is thought she will perform three or four solo songs in the episode, which is scheduled to go out next month.
In her new movie Paltrow plays a fallen country singer, who tries to resurrect her career by going on tour.
In a recent interview with news agency the Associated Press, Paltrow said she researched the history of country music when she accepted the role.
"I sort of started at the beginning with Hank [Williams] Sr. and Johnny Cash and really studied Dolly [Parton] and Loretta Lynn.
"I had never really known very much about country music, and I now am very into it. I know a lot more about it than I did."
The film is released in the US on 22 December and in the UK on 7 January.
