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Christian Pulisic was the star for Milan at the San Siro by setting up Alexis Saelemaekers' opener in the third minute and then doubling the hosts' lead just after the half-hour mark.
The American forward's matching-winning performance against Napoli put Milan in first place on 12 points, ahead of both the title-holders and Roma, on goal difference.
Pulisic was given a standing ovation by supporters when he made way for Davide Bartesaghi just before De Bruyne slotted home the 60th-minute penalty which got Napoli back into the game.
He was taken off by coach Massimiliano Allegri following Pervis Estupinan's red card for pulling back Giovanni Di Lorenzo just as the Napoli man looked set to net from close range.
And from there Milan had to sit back and soak up Napoli pressure as they piled forward in the unuseful hope of keeping their perfect record in Italy's top flight.
