Rhodes, 26, had to overcome a sub-par qualifying effort but had moved into the lead for the first time on Lap 89 of 134.
A late-race wreck involving Kris Wright and Tyler Ankrum bunched the field with Carson Hocevar in the lead, but Rhodes quickly powered back to the front on the restart with 24 laps to go and never looked back.
Rhodes, the 2021 series champion, held off Corey Heim by 2.398 seconds to earn his first win of the 2023 season, which locks him into the series playoffs. He also collected a $50,000 bonus as the winner of the first of three races making up this season's Triple Truck Challenge.
"I don't really know to be honest with you," Rhodes said when asked his truck got so much better at the end of the race. "I didn't think we were that good in practice and we didn't qualify the best.
"It came to life at night. I had so much fun. Charlotte is a track we come to, ThorSport Racing, we're based in Sandusky, Ohio, we come to the North Carolina guys' house and we like to win.
"The whole season is so hard to put together and it's only been getting more difficult over the years. The harder I try I feel the harder it is to win a race."
Dean Thompson ended up third, Hocevar was fourth despite reporting a possible tire problem in the final laps and Grant Enfinger was fifth.
Completing the top-10 were Christian Eckes, Christian Eckes, Matt DiBenedetto, Nick Sanchez and Taylor Gray.
Heim held off a fast-approaching Hocevar by 0.146 seconds to claim the Stage 1 win. Thompson was third, Rajah Caruth was fourth and Zane Smith rallied from 14th to fifth.
Tyler Ankrum (engine change) and Sanchez (unapproved adjustments) both had to start the race from the rear of the field.
Hocevar got around Heim with 15 of 30 laps remaining and cruised to the Stage 2 win.
Thompson ended up third, Smith was fourth and Stewart Friesen rounded out the top five.
Following the break between Stages 2 and 3, the lead-lap trucks all pit with Heim first off of pit road. Caruth (crew member over the wall too soon) and Tanner Gray (did not beat pace car off pit road) had to restart from the rear of the field.
On the restart on Lap 69, Heim was followed by Hocevar and Taylor Gray. Six laps later, Hocevar ran down Heim and reclaimed the lead.
Armani Williams wrecked off Turn 4 while trying to enter pit road which placed the race under caution on Lap 82.
Now in the fuel window to make it to the end of the race, all the lead-lap trucks pit under the caution with Chase Purdy first off pit road thanks to a fuel-only stop. The race returned to green on Lap 90.
Smith got loose off Turn 4 on the restart and triggered a multi-truck incident that also collected Caruth and Hailie Deegan to bring out the fourth caution of the race. Rhodes led the way on the restart with 38 laps remaining.
Five laps later, Hocevar caught Rhodes and passed him to move back into the lead.
Kris Wright and Tyler Ankrum wrecked on the backstretch with 30 laps remaining to bunch the field again.
Hocevar led Rhodes and Heim on the restart only to see Rhodes quickly power around him and back to the lead with 24 laps to go.