The two sides renew hostilities at the Stadio Diego Armando Maradona prior to also meeting Ajax and Rangers in Group A, and the Partenopei have enjoyed a far better opening to their league season.
Match preview
Whispers of a Serie A title charge are still prevalent around Naples, as Luciano Spalletti's side returned to winning ways in ideal fashion against Lazio after dropping four points against Fiorentina and Lecce at the end of August.
The effervescent Khvicha Kvaratskhelia scored his fourth Serie A goal of the season to steal all three points for Napoli, who initially went behind to Mattia Zaccagni's fourth-minute opener before Kim Min-jae restored parity with a header before half time.
Georgia's golden boy Kvaratskhelia sure has taken to the Serie A landscape with aplomb, and the expectation on the 21-year-old's shoulders for the Champions League could hardly be greater as Napoli endeavour to continue their unbeaten start to the season.
A tally of 11 points from their opening 15 on offer sees Napoli sit at the summit in Serie A - ahead of Scudetto holders AC Milan on goal difference - and the Partenopei are now gearing up for their first appearance in the Champions League group stage since 2019-20.
Napoli have endured the pain of two consecutive Europa League last-32 exits in the last two seasons - falling to Spanish pair Granada and Barcelona - but an eight-game unbeaten run at home in the Champions League since November 2017 stands Spalletti's side in good stead.
Jurgen Klopp could only stand and watch as Everton number one Jordan Pickford thwarted his side time and time again in the Merseyside derby, and the Reds boss had his own shot-stopper to thank for keeping the game goalless at Goodison Park.
While Roberto Firmino and Darwin Nunez could not beat the impenetrable wall that was Pickford, Neal Maupay will still be having nightmares about his gilt-edged chance that Alisson Becker kept out, but it was another alarming showing from Klopp's men.
Of course, injuries have not helped the six-time European champions - particularly in the engine room - but picking up just two wins from a possible six leaves them seventh in the table and six points behind current leaders Arsenal at this early stage.
Having failed to win any of their three away games in the top flight so far, a trip to Naples may not fill the Anfield faithful with confidence at a first glance, but Klopp's side remarkably won all six of their Champions League games on the road last term prior to a 1-0 loss to Real Madrid in the final.
That showpiece event will be best remembered for the disgraceful scenes outside the Stade de France both prior and after kickoff, but on the pitch, the wily veteran Carlo Ancelotti and his Blancos side demonstrated their continental nous in a mirror image of the 2018 final.
Napoli and Liverpool are familiar foes having locked horns in both the 2018-19 and 2019-20 Champions League group stages, but the Reds only came out on the correct end of the scoreline in one of those encounters and have failed to score in all three of their visits to the Stadio Diego Armando Maradona.
Napoli form (all competitions):
Liverpool form (all competitions):
Team News
One sour note of Napoli's weekend success over Lazio was the worrying injury to Hirving Lozano, who was stretchered off after a clash of heads with Adam Marusic at the end of the first half, but scans did not reveal any facial fractures.
Nevertheless, the Mexican attacker will surely be spared this week as Matteo Politano prepares to deputise alongside Kvaratskhelia and Victor Osimhen in the final third, but the up-and-coming Giacomo Raspadori is another option for Spalletti.
Lozano is joined in the treatment room by Diego Demme, who needs a bit more time to fully recover from a broken foot, but Spalletti is otherwise well-stocked for the contest as the 63-year-old prepares for another Champions League campaign with a fourth team - he has previously led Roma, Zenit St Petersburg and Inter Milan into battle in the top tier.
Meanwhile, Liverpool's midfield crisis worsened yet again at the weekend, as Fabio Carvalho had to be taken off with a dead leg at half time, and it remains to be seen how quickly the 20-year-old's issue will settle.
Klopp is already without Naby Keita, Alex Oxlade-Chamberlain and Jordan Henderson, but Thiago Alcantara is expected to be back in training early this week and may be able to apply for a place in the travelling squad. With Klopp sure to urge caution over the injury-hit Spaniard, Juventus loanee Arthur could come in for his debut at Napoli.
Elsewhere, Calvin Ramsay, Caoimhin Kelleher and Ibrahima Konate also occupy spots in Liverpool's treatment room, and Klopp should immediately recall Andy Robertson to the side after giving Kostas Tsimikas the nod at Goodison.
Napoli possible starting lineup:
Meret; Di Lorenzo, Kim, Rrahmani, Rui; Zielinski, Zambo Anguissa, Lobotka; Politano, Osimhen, Kvaratskhelia
Liverpool possible starting lineup:
Alisson; Alexander-Arnold, Matip, Van Dijk, Robertson; Elliott, Fabinho, Arthur; Salah, Nunez, Diaz
We say: Napoli 2-1 Liverpool
While the possible introduction of Arthur will only benefit Liverpool on the progressive front, Klopp's attackers have struggled to convince early doors and must now attempt what no Liverpool team has done before - score an away goal against Napoli.