Despite recording a 2-0 win over Arsenal, Napoli have failed to book their place in the knockout stages of the Champions League.
Napoli started brightly in front of their own supporters, with Goran Pandev forcing Wojciech Szczesny to make an early save from a low shot.
Arsenal looked to frustrate the hosts but they still managed to threaten when they broke forward, and Olivier Giroud was denied a goal when his powerful effort was blocked by Rafael Cabral.
Napoli had two good chances to break the deadlock before the break but Jose Callejon curled a shot over from the edge of the box and Christian Maggio failed to hit the target under pressure from Szczesny late in the first half.
Rafael Benitez's side took control of the match in the second half as they looked for the goal which might secure them qualification.
Gonzalo Higuain had a great opportunity to put his side ahead when he collected the ball in the box but he fired a shot over from a tight angle.
However, the former Real Madrid forward made up for his mistake in the 73rd minute as he earned himself some space in the box before drilling the opening goal past a helpless Szczesny.
Napoli were handed a further boost in the closing stages when Mikel Arteta was sent off for a second bookable offence
It looked like the Italian club had secured their spot in the knockout stages but a late winner for Borussia Dortmund in their game against Marseille earned qualification for the Germans.
There was still time for Callejon to score a second in stoppage time, but Napoli missed out on progressing as Dortmund claimed top spot and Arsenal finished second in Group F.