This marks the first time either artist will have been a host for the event billed as "country music's biggest night."
This year's awards show is to be broadcast live from the Sommet Center in Nashville Nov. 12 on the ABC Television Network.
"We are excited to have our reigning (CMA) Male and Female Vocalist host the 'CMA Awards' this year," Tammy Genovese, CMA chief executive officer, said in a statement. "In addition to their musical talent, Brad's quick wit and Carrie's gracefulness will serve them well in this role. CMA is happy to offer both of them their first opportunity to host a nationally televised network awards show."
Both singers are also slated to perform during the event.
"I'm thrilled to have this opportunity to host the awards show," Paisley said. "We're going to have a good time -- start to finish."
"I am so excited to host a show I grew up watching, and am so thrilled to spend this night with the fans and Brad," added Underwood. "It's going to be a party!"