The 25-year-old will be playing a prince in a futuristic drama that is similar in tone to The Hunger Games, Deadline reports.
Peck, who is the grandson of actor Gregory Peck, recently took part in a short arc on another CW show, Gossip Girl, and he was also the lead on ABC Family's 10 Things I Hate About You.
The new show is based on an upcoming book series by author Kiera Cass, set 300 years in the future. It's about a poor girl named America Singer, chosen by a special lottery to compete to marry a prince of a war-torn country.
Aimee Teegarden has signed on to play the romantic lead opposite Peck.
The Selection is one of many new teen-friendly pilots the CW has commissioned for their fall schedule, another being their reimagining of Beauty and the Beast, starring Kristin Kreuk.
The Hunger Games, with which the new pilot shares similarities, opens in cinemas in the US and the UK on March 23.
Watch the trailer for The Hunger Games below: