After graduating from University School in 2003, Mayes attended Dulwich College in London and toured Europe with a singing group.
Two weeks after moving to New York City in 2007, Mayes was hired for a one-episode role in Law & Order: Special Victims Unit. In 2008, he played the lead role in the MTV musical television film The American Mall.
Mayes had guest starring roles on Cold Case, Valentine, Bones, and Medium and played the lead role in the 2010 film Ice Castles.
In 2012, he starred as John in John Dies at the End, which premiered at the 2012 Sundance Film Festival.
After a recurring role on The Client List, he portrayed Matthew Blackwood in the 2013 drama film Burning Blue, which was based on the 1992 play of the same name.
