Roberto Mancini's men needed to defeat Bayern Munich and hope Villarreal could earn at least a point at the Madrigal to qualify for the knockout stages from Group A.
And although City eased past an under-strength Bayern 2-0, goals from Gokhan Inler and Marek Hamsik in Spain kept Napoli in second place and sent them into the last 16.
Napoli made a bright start and missed a glorious opportunity to take the lead in the fifth minute.
Ezequiel Lavezzi's curling cross found Juan Zuniga in plenty of space yet the Colombian hit the ball straight at Diego Lopez from six yards out.
With everything to play for, Napoli continued to look the livelier of the two sides, but could not breach the Villarreal defence in the first half.
That changed on 65 minutes when Inler picked up a loose ball 25 metres from goal before drilling an unstoppable effort into the far corner, leaving goalkeeper Diego Lopez rooted to the spot.
The Italian club secured the three points in the 76th minute after some slack Villarreal defending from a corner.
Ezequiel Lavezzi's ball into the box evaded every yellow shirt and fell to the feet of Hamsik, who bundled it home from two yards out to confirm Napoli's place in the knockout stages.
The news of Napoli's success was a blow for Manchester City fans, who watched their team score an ultimately meaningless 2-0 win over group leaders Bayern.
David Silva put his team in the lead with a terrific strike following a smart touch from Edin Dzeko, before Yaya Toure doubled City's advantage after a nexus of intricate passes which resulted in the Ivorian calmly slotting home in the second half.
Although City put pressure on the German giants from the start, the game started fairly quietly.
Mancini's men began to dictate the tempo; dominating possession as Bayern struggled to get into the game.
City then took the lead via a stunning goal by Silva. The Spaniard was lurking at the edge of the area as Dzeko touched on Gareth Barry's pass from the right wing. The ball sat up perfectly for the Spaniard who lashed the ball home into the bottom corner.
The second goal came just after half time; an exquisite passing move by Mancini’s charges which saw Toure a play a one-two with Silva and then with Dzeko, resulted in the Ivorian finding himself free in the area to tuck the ball under Hans-Jorg Butt.
In the end City's efforts came to nothing though, with Napoli's victory consigning the Sky Blues to third place in the group and a Europa League berth.
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