Frey will appear on an episode set to air in May, Harpo Productions said Tuesday.
Winfrey chose Frey's substance abuse story "A Million Little Pieces," for her book club in September 2005, making it a bestseller.
In January 2006, Frey acknowledged on Winfrey's show that he had lied in the book. Winfrey told him she felt duped and that he had betrayed millions of readers.
Frey's latest book, "The Final Testament of the Holy Bible," will be released this month.
The last episode of "The Oprah Winfrey Show" will air on May 25, bringing an end to what has been television's top-rated talk show for more than two decades.
The Associated Press contributed to this report.