Fernando Llorente gave Juventus a second minute lead and, after goalkeeper Pepe Reina made two stunning saves to keep Napoli in the game, playmaker Pirlo fired a viciously dipping free kick over the Napoli wall into the net from nearly 30 metres in the 74th minute.
He was then upstaged by Frenchman Pogba, who received a pass around 30 metres from goal, flicked the ball up and volleyed in past a bemused Reina six minutes later.
Giuseppe Rossi scored two more goals to help fifth-placed Fiorentina to a 2-1 win over Sampdoria in the evening's other match, taking his tally for the season.
Roma had earlier conceded a 94th minute equaliser at home to Sassuolo as they were held to a 1-1 draw at home by the Serie A newcomers.
Roma lead with 32 points from 12 games, with Juventus on 31 and Rafael Benitez's Napoli on 28 after their second league defeat of the season.
- Sports & Recreation
- Pepe Reina
- Fernando Llorente