Sergio Aguero entered into Manchester City folklore, becoming the clubs all-time top goal scorer with his 178th goal for the club to earn his side an impressive victory away to a resolute Napoli at the Stadio San Paolo.
Key headed goals from defensive duo Nicolás Otamendi and John Stones helped the Premier League leaders to victory, with Raheem Sterling slotting in late on to fire Manchester City to the top of group F, despite neat finishes from Lorenzo Insigne and a Jorginho penalty in an enthralling Champions League tie.
On a highly charged night of football as Napoli welcomed Manchester City to Italy, the home side started the brighter of the two and showed why they have been so dominant in Serie A, with constant pressure in the opening half-hour.
There were early signs of a Napoli goal as in-form Dries Mertens, who seems to have a telepathic link with Argentine forward Insigne, was played through on goal but the Brazilian shot stopper comfortably saved a weak effort.
With Napoli pressing high and suffocating the Citizens midfield, Pep Guardiola cut a dejected figure as his side struggled to keep possession for longer than two minutes. The Serie A leaders continued to show the upper-hand, and it wasn't long before the deadlock was broken, with Insigne capitalising on some lacklustre defending.
The dangerous striker drifted in from the left under no pressure, playing a neat one-two with Mertens, who expertly cushioned the ball into his continuing run, before the diminutive Insigne took his chance, caressing the ball with one touch and curling the ball past Ederson to take the lead.
It took a inconspicuous knock to the knee of key defender Faouzi Ghoulam to disrupt the home sides dominance, as the visitors worked their way back into the game. Aguero had the first chance for Guardiola's men, with Sterling playing in the stocky striker, who wasted a good chance from eight yards out, firing past the post via a deflection.
Stepping up a gear to silence a stunned San Paolo crowd, Manchester City equalised with thirty minutes on the clock, after reworking a corner to their advantage, an excellent floated cross from the impressive İlkay Gündoğan found Otamendi at the back post to rise highest and head home a powerful defender's goal.
With the pendulum swinging in the Citizens direction, on the stroke of half time their was a brief claim for a penalty, as Sterling went down from a light challenge courtesy substitute Christian Maggio, which was waved away by referee Felix Brych.
Starting the second half the brighter of the two, Manchester City had their tails up and the most dangerous player from the first half nearly got the Premier League leaders off to a bright start, as Sterling weaved his way inside the box before a last-ditch tackle from Raul Abiol prevented an second goal for the visitors.
It didn't take long for the Citizens to get a second bite of the cherry, thanks to a brilliant delivery from a Leroy Sane corner. Leaping highest to crash a header off the bar once again, the persistent John Stones bagged his third Champions League goal of the season, although this time luck was now on his side as goal-line technology showed the ball went over the line.
Rattling the crossbar once again, it was the turn of Insigne to smash the woodwork, as the Argentine brilliantly found a moment of space through a delightful change of pace, before spinning on a six-pence to curl a 25-yard strike against the bar as Napoli pushed for an equaliser.
It was the turn of the hosts to change the direction of the game as Partenopei Gli Azzurri pushed and probed to get back into the game. With thirty minutes left on the clock, a lazy swing of the boot from Sane got Napoli level on terms once again. Swiping Abiol with a hacked effort, Brych pointed to the spot, allowing Jorginho to equalise and send Ederson the wrong way.
Again in the spotlight, the officials had another big call to make moments after the Brazilians penalty, as Sterling was in the thick of the action. Gliding past his man to get to the byline, it appeared to be a handball from full-back Elseid Hysaj, but the claims were waived away.
In a match that was more basketball then football with end to end chances within seconds, former Real Madrid winger José Callejón should have given his side the impetus to snatch a victory, but an excellent one on one save from Ederson kept the scoreline level.
So often in football, if you do not finish your chances on the big stage, the top teams will punish you and that was the case for Napoli. Breaking away on the counter attack, Sane paced away from the defence before a excellent challenge from Albiol, but Argentine Aguero finally broke the all-time goal scoring record for Manchester City, by picking up the pieces and comfortably dispatching the ball past Reina to notch his 178th goal for the Citizens in 264 appearances.
To put the icing on the cake in stoppage time, another Kevin De Bruyne assist set up Sterling for the perfect end to the night, as the England international and current top goal scorer settled the outcome of the match in injury time, slotting in past Reina to run away comfortable victors.