City will now be in the draw for the last-16 as they hold a three-point lead at the top, ahead of Shakhtar Donetsk in second spot, while Napoli are a further three points behind, with Feyenoord rock-bottom and pointless.
Lorenzo Insigne had opened for Napoli after 21 minutes with defender Nicolas Otamendi pulling City level on 35 minutes.
The Argentina striker moved onto 178 goals for City - one clear of Eric Brook, who scored 177 goals in 453 appearances from 1928-1940.
Napoli started the better of the two teams and created the first significant chance on goal in the 13 minute when Dries Mertens broke through on goal, but he was thwarted by the City keeper.
The opening goal had been on the cards for some time when it arrived, with Mertens' delightful flicked return pass finding a finish to match from Insigne.
Brook's record-breaking effort came away to Bradford City in September 1938.
De Bruyne took a quick short corner to Ilkay Gundogan and the Germany midfielder flighted an excellent left-footed cross for Otamendi to rise and nod home.
However, it only took the visitors less than 15 minutes to pull back an equaliser and it now stand 1-1 in Naples.
The Italian outfit did equalise just past the hour, however, when Jorginho scored from the penalty spot after Albiol had been brought to the ground by Sane inside the penalty box.
The City goalkeeper had no greater right to save from Jose Callejon when the defensive line in front of him disintegrated in the 68th minute but he spread himself to tip behind.