USA Networks announced Thursday that Cain, 37, will portray the Modesto man accused of murdering his wife, Laci, and their unborn son.
The two-hour original movie has the working title of "The Perfect Husband" and will be shown in the first quarter of 2004, the network said in a statement.
The movie will be from the perspective of two of Laci Peterson's friends and will tell the story of the search for Laci Peterson and subsequent revelations, network officials said.
"'The Perfect Husband' is not just a movie about a specific crime, it's also a movie about our culture," said Jeff Wachtel, a network executive vice president.
Cain is best known for his role in the television series "Lois and Clark: The New Adventures of Superman" and has been hosting the syndicated series "Ripley's Believe It or Not."
Laci Peterson disappeared last Christmas Eve and her remains and that of her fetus were found in April along San Francisco Bay. Scott Peterson said he had been fishing when his pregnant wife disappeared.