AC Milan 1-0 Napoli: Ismael Bennacer hands Milan first leg advantage
The Algeria midfielder struck home from the edge of the area after Braham Diaz broke superbly on the halfway line.
Napoli had Andre-Frank Zambo Anguissa sent off in the second half and were well held by an organised Milan.
Milan also came close to a second goal when Simon Kjaer's header bounced off the underside of the bar.
Napoli, in the Champions League last eight for the first time, were straight out of the traps, demonstrating a belief that comes from being 16 points clear at the top of Serie A.
Georgia winger Khvicha Kvaratskhelia had their best chance of the game in the opening minute after a poor clearance fell at his feet, but his effort from eight yards out was blocked on the line.
Napoli, the highest scorers in the competition this season, continued to push, with former Fulham midfielder Anguissa and Piotr Zielinski having efforts tipped over the bar.
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