Talley's on-screen career began in 2003, with a minor part in the television series As the World Turns. He appeared in four episodes of the drama series Summerland between June and July 2006 as Bryce. The following year, Talley made a guest appearance in the drama film Peaceful Warrior and on the situation comedy series Twins.
In the same year, Talley portrayed Dwight Stifler in American Pie Presents: The Naked Mile, the fifth installment in the American Pie film series. Released direct-to-video, the film earned over US$27 million worldwide. Scott Weinberg of DVD Talk wrote that Talley as Dwight "makes for one of the least appealing movie characters I've ever seen." The following year, Talley again starred as Dwight in American Pie Presents: Beta House, the sixth installment in the series. Released direct-to-video, the film earned over US$18 million worldwide.
Talley was featured in National Lampoon's Van Wilder: Freshman Year as the character Dirk Arnold and also starred as Eric P. Keller in the 2010 DVD movie Hole in One, which had various names prior to release. Recently Talley has moved on to less juvenile movies, landing the lead role of investigative reporter Matt Harper in Deadline, about the racially motivated murder of an African America youth in the South. As well as film credits, Talley has also featured in a British television commercial for Pepsi Max. During Super Bowl XLIV, he drove a car in a Bridgestone commercial about a crazy bachelor party gone wrong. Talley is also featured in a 2010 Pizza Hut ad campaign. It was announced in late June 2012 that he would play Ella Montgomery's (Holly Mariie Combs) love interest on Pretty Little Liars.