Call's first acting role was an uncredited role in the 2005 film The Notorious Bettie Page, followed by roles in the 2006 films The Architect and Beautiful Ohio. In 2007, he appeared in the romantic drama film Evening. He guest-starred in the television series Law & Order: Criminal Intent as Ricky Moss in the episode Neighborhood Watch, and he appeared on Army Wives. In 2009, he appeared in five episodes of the drama series Rescue Me as the adult Connor Gaven. He also joined the cast of NBC's medical drama Mercy. He got a supporting role in the 2009 film Did You Hear About the Morgans? starring Sarah Jessica Parker and Hugh Grant. He appeared in the 2010 independent films Tiny Furniture and Two Gates of Sleep.
In July 2010, Call joined the cast of The CW's young-adult teen drama series Gossip Girl as Ben Donovan, who is connected to two other then-new characters—Juliet Sharp (Katie Cassidy) and Colin Forrester (Samuel Page).
In 2013, he appeared on the NBC drama series Smash as Adam, Jimmy Collins's older brother, and on the USA Network series White Collar.
