He played college basketball for the Villanova Wildcats, where he won national championships in 2016 and 2018, being named Final Four Most Outstanding Player (MOP) in 2018.

As a junior, he averaged 15.8 points, 4.7 rebounds and 2.9 assists per game and played basketball in the Nike EYBL for Team Final.

[4] DiVincenzo appeared in nine games during his true freshman year[5] for Villanova before sitting out with a fractured fifth metatarsal bone in his right foot.

[8] DiVincenzo was named the NCAA Final Four Most Outstanding Player following their championship win over Michigan, in which he scored a career-high 31 points (including five three-point baskets) and recorded five rebounds, three assists and two blocked shots.

[9] DiVincenzo was dubbed the "Big Ragu" by sportscaster Gus Johnson following his last-second tip in a game on January 29, 2017, which gave Villanova the win against the University of Virginia.

When Johnson came up with the nickname, he was probably referring to another "Big Ragu", a character named Carmine Ragusa on the 1970s–80s sitcom Laverne & Shirley, who was also Italian.

[10][11][12] On April 19, 2018, DiVincenzo announced he would declare for the 2018 NBA draft without hiring an agent, thereby leaving open the possibility of a return to Villanova.

[21] He ultimately received a championship ring as he was part of the 2021 team that won the NBA Finals, but did not play in any games after the first round of the playoffs due to a severe left ankle injury suffered against the Miami Heat.

[22] His injury was viewed as a hindrance to Milwaukee's ability to find postseason success, as they had not expected to play role players P. J. Tucker and Pat Connaughton so frequently.

[23][24] On December 25, 2021, DiVincenzo made his return to the court after being out for six months, where he logged 3 points and 2 rebounds in 15 minutes of playing time during a 117–113 win over the Boston Celtics.

[27] On February 12, DiVincenzo scored 7 points and recorded 5 assists in 19 minutes of playing time in his Kings debut, a 123–110 win over the Washington Wizards.

[36] On April 22, 2024, DiVincenzo put up 19 points, including the game-winning three-pointer, in the Knicks' 104–101 victory in Game 2 of the first round of the playoffs against the Philadelphia 76ers.