Gli Azzurri immediately got on the front foot but almost found themselves behind within six minutes as Kenan Yıldız collected Khephren Thuram's pass and Leonardo Spinazzola settled in before being denied by an excellent save from Alex Meret.
The hosts kept coming and looked dangerous in the wide areas, although the Bianconeri handled all the aerial tests well and debutant Randal Kolo Muani showed he could cause problems with good hold-up play before Teun Koopmeiners defused his strike over the crossbar walked.
Matteo Politano came much closer with a striking volley from the edge of the box, and Nico Gonzalez drove forward but roared his shot past the far post.
Juventus then avoided a scare when Manuel Locatelli reached Michele Di Gregorio's Underhit Pass for Scott McTominay. Stanislav Lobotka then sent an ambitious strike marginally over, before two moments to forget for Andre-Frank Zambo Anguisissa proved crucial.
The midfielder rose from a great opportunity and then attempted an interception, but instead touched the ball to Kolo Muani, who finished clinically.
Politano tried to provoke a reaction before the break and came agonizingly close from a free-kick he had won.
Napoli came out defiant for the restart but Romelu Lukaku's header was denied by an excellent Di Gregorio Save.
There was nothing the goalkeeper could do to stop Anguisissa in the 57th minute as he met Politano's cross for Weston McKennie to pick out the bottom corner with a much more clinical header.
Politano and Lukaku then had a post-second effort deflected by Andrea Cambiaso and Federico Gatti, while Gli Azzurri looked ruthless to take the lead.
Scott McTominay earned an opening by luring Manuel Locatelli into conceding a penalty which Lukaku coolly converted by sending di Gregorio the wrong way.
After establishing their lead and was solid to see their seventh consecutive win and move six points ahead atop the Serie A table – although Inter Milan have two games in hand.
They also inflicted the first defeat of Juventus' 22 league games this term, compounding the misery of a side with just one win from their last seven in all matches.
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