Di Vaio also stamped his imprint on the match by drawing a penalty kick and prompting Revolution goalkeeper Matt Reis' dismissal after five minutes.
"Marco's one of those players who, as a striker, doesn't have to be in the buildup and touching the ball fifty times like he's used to," said Patrice Bernier, who converted two penalty kicks in the first half including the one drawn by Di Vaio. "He's paid pretty much to score the goals and make a difference."
Di Vaio reduced the home side to 10 men when he floated behind the Revolution line with the ball, forcing Reis to pull him down.
Referee Sorin Stoica pointed to the spot and then sent Reis off for denying a goal-scoring opportunity. Bernier assumed his usual duties from 12 yards and sent one past substitute goalkeeper Bobby Shuttleworth to place the Impact in front after eight minutes.
New England responded to the early adversity, drawing level on a goal by Diego Fagundez after 26 minutes.
But Bernier restored the lead five minutes later with his second penalty to pull the Impact ahead once more.
Di Vaio ensured the lead by scoring twice on either side of the interval with help from defender Hassoun Camara.
Camara prompted Di Vaio's first goal with a diagonal ball from the middle third. Di Vaio controlled the pass and then cut inside Revolution defender A.J. Soares and scored inside the near post to give the Impact a critical third goal in first-half stoppage time.
Di Vaio scored his second goal of the match — and his league-leading 17th of the season — on another diagonal pass from Camara.
"He is an opportunist," Impact coach Marco Schällibaum said of Di Vaio. "He is a goal-maker, he is a machine, like a terminator. I told him before the game he was a terminator and we need him again. He is crazy, but I am very proud to have this guy."
Kelyn Rowe produced a consolation goal for the Revolution in the 76th minute, but the Impact played out the waning stages of the match with the knowledge that the three points — and the corresponding return to first place in the Eastern Conference on the goals-scored tiebreaker over New York and Sporting Kansas City — were safe.
"For us, it was a great result to have three points," Bernier said. "The distance is there between (us) and those fourth and fifth places. Now it's really the top three teams that are really going away."
Montreal will attempt to maintain its lead of the Eastern Conference when it opens a two-match homestand with Columbus at Stade Saputo on Saturday.