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"Ashlee will be playing 'Lia Wickfield' and Pete will be playing 'Chester Bryon'. They are a 'Bonnie and Clyde'-like couple," a source tells PEOPLE.
Ashlee is scheduled to begin filming her scenes Friday. Pete is expected to start shooting the show sometime next week.
The popular CBS show has been a celebrity guest magnet, welcoming Craig T. Nelson, Rumer Willis and Nelly.
Entertainment Weekly's Michael Ausiello was first to report the news.
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