Also set to perform at the show are Idina Menzel, Alison Krauss, Little Big Town, The Flaming Lips and several other acts and special guests.
Rogers said it is likely he and Parton would perform their 1983 hit "Islands in the Stream."
"As I'm bringing this chapter of my career to a close, this will be an unforgettable way to celebrate with my talented friends, who I'm so grateful to have crossed paths with. It means so much that they would feel compelled to do this for me. Of course, the night would not be the same without Dolly Parton being part of it. We've enjoyed a special friendship for decades, and I'll forever look back fondly on the many collaborations, performances, and laughs we've shared as some of the most extraordinary moments of my career. I know it will be a moving experience for us standing on that stage together for one last time," said Rogers.
Parton added, "Kenny is like a family member to me. We have been friends for over 30 years and made musical magic together. Since 1983, when we released 'Islands in the Stream,' everyone has had an expectation to see Kenny everywhere I go and me with him wherever he goes. Well, I guess for many of those fans that wanted to see us together, this will be that night. Performing with Kenny for the last time ever on October 25th is going to be emotional for both of us, but it's also going to be very special. Even though Kenny may be retiring, as he fades from the stage, our love for each other will never fade away."
Rogers has 24 No. 1 hits in his career and is a three-time Grammy Award winner.