Maye committed to the University of North Carolina without knowing if he would receive a scholarship. Before he enrolled, he was informed by head coach Roy Williams that he would be on full scholarship. He was seldom used as a freshman.
Sophomore season (2016–17)
In Maye's sophomore season, he recorded his first 10-point game coming off the bench against Davidson in December. Despite only having three 10-point games during the regular season, Maye had three more 10-point games during the NCAA Tournament. In the Elite 8 game against Kentucky, Maye hit the game-winning jump shot with 0.3 seconds left in the game, shortly after Malik Monk hit a three to tie the game at 73 with 7.2 seconds left. He also had a career-high 17 points in this game. For his performance in the South Regional, he was named to the South Regional all-tournament team and won the regional's Most Outstanding Player award. North Carolina went on to beat Oregon and Gonzaga to win the 2017 NCAA Men's Basketball National Championship. He finished the season averaging 5.5 points per game.
Junior season (2017–18)
Maye had a breakout season as a junior in the 2017–18 season. In his first nine games, he averaged 20.8 points and 10.3 rebounds per game. This is the best start by a Tar Heel since Tyler Hansbrough's senior year in 2008-09. He ended up averaging 16.9 points per game and leading the team with 10.1 rebounds per game. On April 23, 2018, Maye declared for the NBA draft without hiring an agent. On May 24, Maye announced his intention to return to UNC for his senior season.
Senior season (2018–19)
Coming into the season Maye was nominated for many preseason awards including preseason ACC player of the year. On February 5, Maye tallied 31 points and 12 rebounds in a 113-96 win against NC State. On February 21, Maye scored 30 points and 15 rebounds in a 88-72 victory over rival Duke.
Professional career
On June 21, 2019, the Milwaukee Bucks signed Maye to their Summer League team. On October 14, 2019, Luke Maye was waived by the Bucks, but was assigned to the Bucks’ NBA G League affiliate, the Wisconsin Herd. Maye was sidelined with an injury from December 16 to January 14, 2020. On March 7, Maye posted 25 points, nine rebounds, two assists, one block and one steal in a 136-122 win over the Capital City Go-Go. He signed with Dolomiti Energia Trento of the Italian Lega BasketSerie A on July 18.