Martin, who quarterbacked the Vols to the 1998 national championship, was Tennessee's assistant head coach, passing game coordinator and receivers coach the past two seasons under Jeremy Pruitt, who was fired on Jan. 18.
Martin's contract with Tennessee expired at the end of last month, just a few days after Josh Heupel was hired as Tennessee's new head coach.
Heupel is expected to hire Kodi Burns as the Vols' new receivers coach.
Before returning to his alma mater, Martin was the offensive coordinator at USC and had been on the Trojans' staff since 2012.
With the Ravens, Martin replaces David Culley as the wide receivers coach. Culley was named the Houston Texans head coach last week.
Baltimore has one of the youngest wide receiver groups in the NFL. None of the wide receivers under contract next season for the Ravens are over the age of 24, and starters Marquise "Hollywood" Brown and Miles Boykin are entering their third seasons.
"Tee is a natural, charismatic leader, whose bright offensive mind will benefit our young group of wideouts," Ravens coach John Harbaugh said. "His history of coaching standout receivers on the collegiate level will translate well to the NFL."
Information from ESPN's Jamison Hensley was used in this report.