The "Hannah Montana" co-stars previously appeared on the Country Music Association Awards show in 2006.
"The 42nd annual CMA Awards" presentation is to be broadcast live from the Sommet Center in Nashville Nov. 12 on the ABC Television Network.
Performers for the show announced Monday are Jason Aldean, James Otto and Martina McBride.
Additional presenters include Heidi Newfield, Darius Rucker, Josh Turner and Lee Ann Womack. Previously announced performer Taylor Swift will also present an award, ABC said.
Other previously announced performers include co-hosts Brad Paisley and Carrie Underwood, along with Trace Adkins, Rodney Atkins, Brooks & Dunn, Kenny Chesney and The Wailers, the Eagles, Alan Jackson, Kid Rock, Lady Antebellum, Miranda Lambert, Kellie Pickler, George Strait, Sugarland and Keith Urban. Academy Award-winning actress Reese Witherspoon was previously announced as a presenter.
In addition to presenting an on-air award, Newfield will also co-present the pre-telecast awards, including the CMA Broadcast Awards, with Premiere Radio Networks radio personality Blair Garner, host of "After Mid-Nite with Blair Garner."