K'Naan and Colombian singer Juanes have also been added to the list of performers who will take to the stage at 'A Decade of Difference: A Concert Celebrating 10 Years of the William J Clinton Foundation' at the Hollywood Bowl in Los Angeles on October 15.
Lady GaGa, U2's Bono and The Edge, and Usher were previously announced as performers at the event, which will also serve as a birthday celebration for Clinton.
In a statement, the former president said that he is "deeply grateful that the artists associated with the concert are giving their time and talent to raise awareness" of the work done by his Foundation.
"In the past decade, commitments to my Clinton Global Initiative have improved the lives of more than 300 million people around the world," he continued.
"We've lowered the cost of AIDS and HIV treatment, combated climate change, strengthened economies, increased access to education and healthcare, provided financing and mentoring for small businesses."
Clinton added: "This celebration marks ten years of these efforts and demonstrates of how much we can do to make a difference in the years ahead."
The concert will be live-streamed on Yahoo!
Chesney is among the artists who have been nominated at the upcoming 45th annual Country Music Association Awards, which takes place in November.
Watch Kenny Chesney's music video for 'You and Tequila' featuring Grace Potter below: