Gli Azzurri took the lead straight away but were almost behind within six minutes when Kenan Yıldız collected Khephren Thuram's pass and set up Leonardo Spinazzola before being denied by a brilliant save from Alex Meret.
The hosts kept coming and looked dangerous in wide areas, although the Bianconeri passed all aerial tests well and debutant Randal Kolo Muani showed he could cause problems with good hold-up play before Teun Koopmeiners fired his shot harmlessly over the bar .
Matteo Politano came much closer with a striking volley from the edge of the penalty area, and Nico Gonzalez drove forward but sent his shot past the post at the other end.
Juventus then avoided a scare when Manuel Locatelli reached Michele Di Gregorio's under-hit pass for Scott McTominay. Stanislav Lobotka then sent an ambitious strike marginally over, before two moments to forget for Andre-Frank Zambo Anguissa proved crucial.
The midfielder headed over from a great chance, then tried to intercept but hit the ball towards Kolo Muani, who finished clinically.
Politano tried to provoke a reaction before half time, coming painfully close after winning a free kick.
Napoli came out defiantly for the restart, but Romelu Lukaku's header was denied by an excellent save from Di Gregorio.
However, the goalkeeper could do nothing to deny Anguissa in the 57th minute as he met Politano's cross for Weston McKennie and headed home with a much more clinical header to find the bottom corner.
An effort from Politano and Lukaku was then deflected by Andrea Cambiaso and Federico Gatti respectively, as Gli Azzurri seemed to take the lead relentlessly.
Scott McTominay earned an opening by tricking Manuel Locatelli into conceding a penalty, which Lukaku coolly converted by sending Di Gregorio the wrong way.
After establishing their lead, Napoli were solid to record their seventh straight win and move six points clear of Serie A – although Inter Milan still have two games in hand.
They also inflicted the first defeat in Juventus' 22 league matches this season, adding to the woes of a side with just one win from their last seven games in all competitions.
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