Napoli condemned last season's Champions League runners-up Borussia Dortmund to their first defeat of the season on Wednesday as the Germans' European campaign endured a disastrous start.
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Gonzalo Higuain and Lorenzo Insigne grabbed the goals in the Italians' 2-1 Group F win after Dortmund had goalkeeper Roman Weidenfeller red-carded on the stroke of halftime, with coach Jurgen Klopp also sent to the stands.
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Napoli soaked up early pressure from the Germans who went into the match with a perfect record of five wins in the Bundesliga and not having lost a match since their Champions League final defeat to Bayern Munich in May.
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Marco Reus slid a fine pass through for Robert Lewandowski in the 26th minute, but the Polish striker's left-foot shot was well-saved by Pepe Reina.
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Sven Bender then saw his volley from the edge of the box take a deflection over the crossbar.
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Napoli grabbed the lead on the half-hour mark.
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Camilo Zuniga crossed from the left for Higuain to get in front of Marcel Schmelzer and head the ball into the bottom corner beyond the dive of Weidenfeller.
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It was the Argentine striker's second goal in successive games at the Stadio San Paolo, after netting in the weekend win over Atalanta, and his third in three games.
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Klopp was so incensed by the goal that he was sent to the stands for his protests.
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Ten minutes before the break, Reus volleyed wide of the target before the night got even worse for last season's runners-up.
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Captain and goalkeeper Weidenfeller came rushing off his line to deny Higuain but was sent-off for handling outside the area.
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Australian goalkeeper Mitchell Langerak came on to replace Weidenfeller and he was straight into action having to stop Higuain's low free-kick.
Borussia Dortmund will just have to improve in their next game cos they must win that to be on the safe side.