Jerel McNeal scored 14 points, and Maurice Acker had 12 for Marquette (21-6, 11-5 Big East). The Golden Eagles won their fourth game in a row.
Scottie Reynolds led Villanova (17-10, 7-8) with 14 points, while Dante Cunningham and Corey Stokes each scored 13.
The Golden Eagles went 10-for-23 from 3-point range; Villanova was only 2-for-15.
The Wildcats had won four of five overall, including a 67-65 victory over then-No. 13 Connecticut on Saturday, that again energized their hopes for a possible NCAA tournament at-large bid. A win over the Golden Eagles would have been a huge boost to their confidence and RPI, especially with a game Saturday at No. 13 Louisville.
Now, Villanova's bid for a fourth consecutive NCAA tournament appearance is a long shot.
They blew an early second-half lead mostly because of a season-high 23 turnovers. They flopped on some ill-timed bad passes that either sailed out of bounds or were converted into easy baskets by Marquette.
Two costly turnovers came midway through the second half that allowed Marquette to grab a double-digit lead and take control of the game.
David Cubillan stole a pass under the basket -- Villanova's 20th turnover -- and scored on an easy layup. Cunningham was whistled for goaltending on the next possession to help Marquette take a 68-58 lead.
But the Golden Eagles ended the rally in a hurry.
Acker and James hit consecutive 3s, and James followed a Villanova basket with another 3-pointer that gave the Golden Eagles a 62-56 lead.
Stokes scored 11 points in the first half to help the Wildcats take a 39-32 lead.
A COACH REMEMBERED: Ted Kjolhede, the winningest coach in Central Michigan history, has died. He was 84.
The school said Kjolhede died Sunday at his Mount Pleasant, Mich., home.
A cause of death was not released.
Kjolhede won 216 games in 15 seasons with the Chippewas starting in 1956.
He moved into the athletic director's job in 1972 and served until retiring in 1984.
He was instrumental in the Chippewas' rise from Division II to Division I and its admission into the Mid-American Conference.
Kjolhede earned letters in football, basketball and tennis at Central Michigan, graduating in 1948.