The NBC show, produced by Jerry Seinfeld, features a real-life couple who have had an argument and asks a group of celebrities to decide who is in the right.
TV Guide reports that Midler will appear on the panel alongside Deal Or No Deal host Howie Mandel.
The series, which was recently renewed for a second season, has previously featured stars including Eva Longoria Parker, Alec Baldwin, Sheryl Crow and Madonna on its panel.
Gwyneth Paltrow is also expected to appear on the show in the future.
Midler's episode is currently scheduled to air on May 13.