The papers filed in a county courthouse in Franklin, Tenn., cited irreconcilable differences.
Aldean -- whose hits include "Big Green Tractor," "The Truth" and "Don't You Wanna Stay" -- was photographed in September acting inappropriately with Season 11 "American Idol" contestant Brittany Kerr at a Los Angeles club.
He issued a public apology, saying: "I screwed up. I had too much to drink, let the party get out of hand and acted inappropriately at a bar."
The Aldeans tried to patch things up, appearing together at November's Country Music Association Awards, but failed to work past the singer's cheating scandal, celebrity news website TMZ said.
"This is a really tough time for my entire family," Aldean said in a statement.
"Jessica and I have been together since we were teenagers. We've been through a lot of ups and downs over the years as we grew up together as a couple. She will always be important to me because she is the mother of my children, and I know that we will both always make our daughters our #1 priority.
"I've learned that everyone always rushes to judgment when they hear news like this," he added. "That's really hard because no one knows anything about our relationship but us. I understand that because of my job, I have to go through a lot of this in the public eye, but for my girls' sake I really wish people would give us some level of privacy and at the very least be respectful of them."
Aldean, 36, and Ussery, 33, are parents of daughters Keeley, 10, and Kendyl, 5.
2014: The Year in Music [PHOTOS]