The drama, which is being executive produced by Gossip Girl showrunners Josh Schwartz and Stephanie Savage, focuses on a group of young people working in Washington.
Deadline reports that Kodjoe has now signed up to play the President's senior adviser, who is said to be very intelligent.
Kodjoe starred in the NBC drama Undercovers this season but the show was axed in November. He has previously appeared in shows including Soul Food, Boston Public and Crossing Jordan.
Georgetown, which is in contention for ABC's 2011-2012 season, also stars Kevin Zegers, Joe Mazello, Condola Rashad, James Wolk, Katie Cassidy and Daisy Betts.