The Argentine defender grabbed a goal and an assist to give Walter Mazzarri's men a 3-1 victory over Cesena who played the majority of the second half with ten men
The experienced defender showed great awareness to pick out Ezequiel Lavezzi with a long throw in the third minute before Roberto Guana equalised 22 minutes later. Cesena were reduced to ten-men in the 55th minute and the away side took full advantage of the sending off 12 minutes later when Campagnaro slid the ball home from close range.
Marek Hamsik put the game beyond doubt when he slammed the ball past the helpless keeper with two minutes left on the clock.
Napoli's victory ensures the club go top of Serie A following the 2-2 draw between AC Milan and Lazio on Friday evening and the rest of the league playing on Sunday.
The away team made a superb start to the game and were ahead in the third minute. Hugo Campagnaro's long throw caught out a slow Cesena defence as the unmarked Lavezzi controlled the ball before slamming it past goalkeeper Nicola Ravaglia from eight yards out.
However, the home side were on level terms in the 25th minute when summer signing Roberto Guana levelled the scoring. Eder used his pace to get clear down the right wing before playing an inviting low cross into the box that was directed into the net by Guana, despite Morgan De Sanctis getting his fingertips to the ball.
Coach Walter Mazzarri's men threatened to re-take the lead in the 36th minute but Lavezzi could not add a second. After a slick passing move, Mario Santana picked out the Argentine who narrowly missed the target from close range.
Cesena also came close to taking the lead in the final minute of an entertaining first-half. Eder found space once again on the right wing and his chipped ball into the box found Antonio Candreva who saw his volleyed effort from a tight angle saved by De Sanctis.
During the second half the home side were reduced to ten-men in the 55th minute when Yohan Benalouane saw his second yellow card of the game for a deliberate handball before being given his marching orders.
Napoli were able to take advantage of their extra man in the 67th minute when Campagnaro slid the ball home from close range. Lavezzi cut his corner back to Marek Hamsik and he picked out the Argentine centre-half, who made it 2-1.
In the 85th minute, substitute Goran Pandev missed an open goal that will be an early season contender for miss of the campaign. After a good passing move from Napoli, the ball was squared to the on-loan striker, but he hit the crossbar from six yards despite the goal being at his mercy.
Napoli wrapped up the points in the 88th minute when Hamsik made no mistake on slamming a ferocious effort past the 'keeper from 18 yards out following a poor clearance from Steve Von Bergen.
Mazzarri's men will next be in action on Wednesday evening when they kick off their Champions League campaign with a tricky trip to face Manchester City.