The Friday Night Lights star will play an arson investigator on the CBS drama, TVLine reports.
Saved from a fire by Tony (Michael Weatherly) years before, Charles's character Jason is still haunted by the death of a family member.
The character was previously referred to in the show's ninth season premiere, with mention of a "kid from Baltimore" in Tony's past.
"Many of the people involved with NCIS were big Friday Night Lights fans, so having Gaius join us is a genuine pleasure," said NCIS exec Gary Glasberg. "We are thrilled to have him on board and look forward to everything he brings to the role."
Charles, who played Brian 'Smash' Williams on Friday Night Lights between 2006 and 2008, has since appeared in Angelina Jolie film Salt and an episode of ABC's Pan Am.
Other forthcoming NCIS guest stars include Jocko Sims (Dreamgirls) and Karina Lombard (Rescue Me).