The three-time CMA winning country star has not performed on the awards telecast since 2006.
Show officials said in a press release that Hill has a new album due to come out early 2012. It will be her first studio album since 2005's "Fireflies."
Hill joins a star-studded lineup that includes Taylor Swift, Jason Aldean, Brad Paisley, Blake Shelton and Keith Urban. All five are entertainer of the year nominees.
Lady Antebellum, Miranda Lambert and The Band Perry will also perform.
Paisley, the reigning entertainer of the year, will host the awards with Carrie Underwood.
The show airs Nov. 9 on ABC from Nashville.
The Associated Press contributed to this report.