The 66-year-old, who has won multiple Grammys, will pay tribute to Liberace, whose HBO biopic "Behind the Candelabra" was nominated for 15 Emmys.
Michael Douglas and Matt Damon, who were nominated for their roles in "Behind the Candelabra," were previously announced as presenters.
John is set to release a new album, "The Diving Board," on Sept. 24. It is his first studio album in seven years.
The 65th Primetime Emmy Award will be hosted by Neil Patrick Harris and air Sept. 22 on CBS.