Veteran striker Miroslav Klose helped himself to two goals as Lazio crushed Fiorentina 4-0 in the other game, a result that boosted their chances of reaching next season's Champions League.
Juventus struggled to break down Sassuolo for 82 minutes and appeared to be running out of ideas until Pogba, who himself had just been booked after showing signs of frustration, broke the deadlock.
The Frenchman, showing superb control, collected Simone Pepe's pass and, without breaking stride, volleyed past Andrea Consigli from the edge of the area with his second touch.
The win took Juventus onto 61 points from 26 games, while fading AS Roma, who are second, have 50 after their goalless draw at Chievo on Sunday.
Lucas Biglia set Lazio on their way and an Antonio Candreva penalty put them in complete control as they went joint third with Napoli on 46 points.
Fiorentina, whose Champions League hopes took a hefty blow as they dropped four points behind their opponents in joint fifth, were unrecognisable from the team that won 2-1 at Juventus in the Italian Cup on Thursday.
The top two qualify for the Champions League group stage and the third-placed club go into the final playoff round.
Argentina midfielder Biglia began the rout when he volleyed home from the edge of the penalty area after six minutes.
Lazio then missed a flurry of chances but it was all over when Nenad Tomovic tripped Felipe Anderson and Candreva converted the penalty before being booked for a shirtless celebration in the 65th minute.
The third goal started from a Fiorentina free kick at the other end of the pitch.
Matias Fernandez gave the ball straight to a Lazio defender who set Candreva clear on the right and, although his shot was saved by Norberto Neto, Klose headed in the rebound.
The 36-year-old German also grabbed the fourth at the second attempt after his initial effort was stopped by Neto, his eighth league goal of the season.
(Writing by Brian Homewood in Berne; editing by Justin Palmer)
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