Smith, a 6-foot-1, 185-pounder, worked out for the Volunteers and impressed the Vols coaching staff running a 4.5 40-yard dash.
"I went to work out with them and it was awesome," Smith told InsideTennessee. "They gave me the offer and I was so excited."
Smith's commitment comes on the heels of teammate and offensive lineman Brett Kendrick's commitment, which took place during Tennessee's offensive/defensive line camp over the weekend.
"Brett was really excited," Smith said. "We were talking about roommates and stuff like that, but at the same time we were talking about hoping that Charlie (High) gets an offer too. It is in the Lord's hands though and I know he has something planned. We will just see what happens."
Charlie High is the rising senior quarterback for Christian Academy of Knoxville and is scheduled to work out for the Volunteers in the coming weeks to determine whether he is worry of an offer from the Orange and White.
However, the Vols newest commitment thinks a trio of CAK athletes good be a great thing for the Tennessee program.
"I think it would be great to have all three of us playing there," Smith said. "Three Tennessee guys playing there would be awesome. It would be cool to reunite in college. I think all three of us playing together would just bring good things. We have been best friends forever. I think that would bring a lot to the Tennessee program."
Smith, who snagged 96 receptions for 1,911 yards and 22 touchdowns during his junior season, considers himself to be a cerebral receiver with crisp routes.
"We run a spread at CAK and I am the outside receiver," he said. "I am pretty much a deep-ball guy and I like to get the ball in space. I think of myself as a smart football player, I know my routes and I know how to run them."
The Knoxville, Tenn., native has orange blood and says it just got a little bit thicker.
"I have grown up a Tennessee fan," he said. "I have been at Tennessee all my life, I haven't been a diehard Tennessee fan, but I am definitely about to be."
You can see highlights from Smith's junior campaign below courtesy of James W. Smith: