The playmaker will be pulling the strings for Bosnia-Herzegovina at next year's World Cup, the country's first, but Rudi Garcia's Roma are the club side fortunate to have the 23-year-old in their ranks.
Napoli, under the watchful eyes of former star Diego Maradona, began the match two points off the pace and hoping to upset Rudi Garcia's early season pacesetters.
However, Rafael Benitez's men spurned two good chances in the first half when both Goran Pandev and Lorenzo Insigne missed the target from scoring positions.
After Pjanic's curling free kick gave Roma a 1-0 lead late in the first half, the Bosnian midfielder made it two - this time from the spot - after Napoli defender Paolo Cannavaro saw red for a clumsy challenge on Marco Borriello.
Roma now sit summit with a maximum 24 points from eight games with Napoli, conceding their first defeat of the season, losing second place to Juventus, who visit Fiorentina on Sunday.
Having equalled Juventus's record streak of eight opening wins under Michel Platini, Garcia admitted Roma's eighth win made up for losing captain Francesco Totti to a suspected thigh injury in the first half.
"I'm glad with the win, but it comes with us losing our captain to injury. But tonight the Roma of Totti has equalled the Juventus of Platini," Garcia told Sky Sport Italia.
"He (Platini) was one of the greats. It's friendly to be in this position."
It capped an eventful day for Maradona, who helped Napoli to their only two league titles in 1987 and 1990, but on Friday was served a 39-million-euro ($53-million) tax bill, which he still disputes.
After leaving minutes before the final whistle, Maradona was reported to have said by domestic news agency ANSA: "Emotional? Do I see emotional? We lost. It's a shame I'm no longer playing."
Pandev anyhow spurned Napoli's best chance of the half after escaping his marker in midfield to run on to Insigne's superb long ball.
The striker was positive upon goal but former Napoli 'keper Morgan De Sanctis shut down the angle and got a hand to Pandev's shot, which was then cleared acrobatically by Daniele De Rossi.
Roma, however, had the momentum.
Florenzi's angled low drive went just a metre broad of Reina's upright and Gervinho had claims for a penalty waved away after he tumbled in the place as he cut in from the left.
Kevin Strootman then saw a drive from distance just sail over the bar.
Insigne spurned a second great chance for Napoli when he sent his low shot from close in off the post after evading a clumsy challenge from Maicon.
Roma finally broke the deadlock late in injury time, Pjanic stepping up to send a sublime curling free kick past Reina after Gervinho had been upended and won a free kick 25 metres out.
Napoli dominated the opening exchanges after the restart and Gokhan Inler almost levelled with a superb first-time steer the came off de Sanctis's upright.
But there was never much threat from Benitez's men, who appeared to be missing the power and drive of Gonzalo Higuain.
Maicon showed fine skill deep upon the right to squeeze between two defenders and send in a low cross for Florenzi which the forward narrowly missed.
Higuain finally made his appearance upon 68 minutes, replacing Pandev, but Napoli suffered a blow moments later when Cannavaro was sent off for manhandling Borriello in the place.
Pjanic made no error from the spot, sending Reina the wrong way with a powerful shot that rocked the back of the net.
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