William Morrow, a division of HarperCollins, will publish "The Billy Bob Tapes: A Cave Full of Ghosts" on May 15, The Hollywood Reporter said.
The book, with a forward by Jolie, will include "colorful tales of his modest Southern upbringing, his bizarre phobias, his life, his loves [including his heartbreakingly brief marriage to fellow Oscar winner Jolie], and, of course, his movie career," the publisher said Thursday.
Thornton and Jolie were tabloid fodder as each wore a vial containing the other's blood on a necklace during their marriage from 2000-2003.
Thornton, who has remained on good terms with Jolie since their divorce, has denied his next film, "And Then We Drove," is based on their relationship.
"I would never make a movie about my best friend, either, or any other ex of mine, or something," he told New York Magazine. "That's not my bag. I don't mind exposing myself, but I'm certainly not gonna make a movie about someone else."