With neither team creating any clear cut chances in the opening quarter of an hour, the first real incident of the match was the substitution of Naby Keita after just 18 minutes. Though there appeared to be no impact or tackle that caused Keita's injury, the midfielder had to be stretchered off, to the worry of Liverpool fans.
In truth, the first half was ultimately a showcase of late tackles and yellow cards. Neither team's attackers linked up as they so often have in the past, and 0-0 was a fair scoreline going into half time.
Though the hosts started the second half on the front foot, the flow of the game was much the same as the first half. Centre backs snuffing out any danger and forwards not taking care of the ball in promising positions.
The game finally burst into life with 10 minutes to go, as a Mario Rui cross found substitute Dries Mertens in space, but the Belgian could only shin the ball onto the crossbar from eight yards out.
The hosts would score a well deserved winner just 30 seconds from time, after Jose Callejon got in behind Andy Robertson and crossed for Lorenzo Insigne, who slid in to apply the finishing touch from six yards out. Zero shots on target told the story for Liverpool, who deserved nothing from the game.
Key Talking Point
Although the onus was on the hosts to gain a crucial three points at home, and therefore take the game to Liverpool, Napoli showed that their defence is just as impressive as their potent front three.
In a game where chances were few and far between, Napoli's back four seemed impenetrable at times. The Italians kept one of Europe's most potent attacks quiet for the majority of the game and appear to be a solid outfit under Carlo Ancelotti.
Starting XI: Ospina (6); Maksimovic (7), Albiol (7), Koulibaly (7*), Mario Rui (7); Allan (6), Hamsik (6), Fabian (5); Callejon (7), Milik (5), Insigne (7).
Substitutes: Verdi (5), Mertens (6), Zielinski (N/A).
STAR MAN - Kalidou Koulibaly
Imperious both in the air and on the ground, Koulibaly never even gave Mohamed Salah a sniff of goal.
The Senegalese centre back frequently out paced Liverpool's front three, and his positioning and choice of tackles were near perfect. A lunge late in the first half which saw him carded was the only negative in an impressive display.
WORST PLAYER - Arkadiusz Milik
Unfortunately for Milik, this game wasn't set up for him to be effective. Too static most of the time, the Polish forward didn't drag van Dijk or Gomez out of position enough.
When he did receive the ball his decision making was far from ideal and he was eventually replaced by Dries Mertens. It's no coincidence that Napoli looked more fluid when he departed.
Key Talking Point
With plenty of talk surrounding Liverpool's front three and their lack of fluidity this season, an away game where the Reds could play on the break should've been perfect for Mohamed Salah, Sadio Mane and Roberto Firmino.
The reality was far different however, and the front three never looked like they were on the same wavelength. Talk of disconnect between the three of them will no doubt continue after this showing.
Starting XI: Alisson (6); Alexander-Arnold (5), Gomez (7*), Van Dijk (7), Robertson (6); Milner (6), Keita (N/A), Wijnaldum (6); Salah (5), Firmino (6), Mane (6).
Substitutes: Henderson (6), Fabinho (N/A), Sturridge (N/A).
STAR MAN - Joe Gomez
This could have gone to either of Liverpool's centre backs who were both superb. Gomez just edges the star man fight though because of his relative lack of experience at this level.
The Englishman looked completely at home playing at the highest level, and his understanding of the game paired with his obvious physical gifts made him difficult to get the better of.
WORST PLAYER - Mohamed Salah
It's now getting to the point where Salah is so desperate to score that he's becoming a detriment to the team.
The Egyptian found himself in promising positions few times, but when he did pick up the ball in dangerous areas, he was far too predictable.
Liverpool will welcome Red Star Belgrade to Anfield as the Reds look to bounce back from this disappointing showing. Napoli have the unenviable task of a trip to Paris to face Neymar and co.