TV Line says that the former Without A Trace star will appear in multiple episodes of the show as Ziva's boyfriend, CIA agent Ray Cruz.
NCIS' executive producer Gary Glasberg described Ray as a "fun, smart, exciting addition".
He added: "We can't wait to watch Enrique bring him to life and interact with the NCIS team."
Murciano has also appeared in episodes of Medium and CSI: Crime Scene Investigation. He was originally attached to the medical drama Off The Map but left for creative reasons.
He is expected to make his NCIS debut in the 20th episode of the season. The show continues on Tuesdays at 8/7c on CBS.