The Giallorossi skipper delivered a decisive blow with a blistering 25-yard drive that gave the capital club its first Serie A win of 2013.
Francesco Totti scored the only goal of the game in the 58th minute, with the Giallorossi captain finding the top left corner of Gianluigi Buffon's goal with an unstoppable 25-yard drive.
Juventus tried to rally in the remaining half hour but a blunt Bianconeri outfit was unable to force an equalizer, meaning Napoli can now cut the lead at the summit of the standings to just two points should the Partenopei defeat Sampdoria at home on Sunday.
Despite its woeful recent form, Roma began in a sprightly fashion, with Pablo Osvaldo looking particularly lively up front. The volatile forward threatened twice inside the opening 10 minutes, cutting inside Leonardo Bonucci early on only to shoot straight at Buffon, before then being forced too far wide by the Juventus skipper to get a shot away, after being slipped through by Erik Lamela.
Juventus, despite its Champions League exertion in midweek, also played their part in what was an open start to the game, with Andrea Pirlo nearly opening the scoring with a clever free kick that could very easily have found its way into the bottom right corner of Maarten Stekelenburg’s goal had the Dutchman not got down so swiftly to parry the ball to safety.
The pace of the game then dropped and the atmosphere became increasingly tetchy. Daniele De Rossi levelled Stephan Lichtsteiner with a desperately late lunge on the Swiss wingback before Totti elected to run his studs down the leg of Pirlo, leaving the playmaker with a nasty gash on his knee.
The halftime break removed some of the mounting tension from the game, allowing both sides to rediscover their attacking instincts. First, Osvaldo hooked the ball just wide after sliding to get on the end of Totti's through ball, and then, just moments later, Mirko Vucinic whizzed a volley just past Stekelenburg's right post.
The game-breaking goal arrived just before the hour mark and in sensational fashion. Miralem Pjanic tried his luck with a free kick but it was blocked by the Bianconeri wall. The ball only went as far as Totti, though, and he unleashed a blistering, first-time shot that gave Buffon absolutely no chance.
Juventus pushed forward in search of an equalizer, but it was Roma that looked the more likely to score next, and it was only a combination of poor finishing and wonderful defending that prevented the captial club from doing so. De Rossi erred after being teed up by Osvaldo, before Lichtsteiner threw his body in the way of an effort from Marquinho.