This is a team that Liverpool will know all too well as they faced each other last season in the competition and also having played each other in the Red's last two pre-season campaigns.
The Italian side won 1-0 last year in the Champions League. Lorenzo Insigne scored a 90th-minute winner last season in a game that failed to get going. Liverpool set up with the aim to get a draw and late defensive errors ultimately cost them the points.
This season, the European champions will be looking to perform better on the hostile away ground in Naples.
Form going into the match
Liverpool have kept a 100% win rate so far in the Premier League, winning their first five games this season. The Reds extended their win domestic record to 14 league games, which is a club record.
Jurgen Klopp’s side have also already claimed their first piece of silverware this season, beating Chelsea in the UEFA Super Cup on penalties to claim the German's second trophy with the Reds.
Napoli currently sit fifth in the Serie A and have won two of their first three games. However, they did lose their second game, losing 4-3 to champions Juventus.
Belgium forward, Dries Mertens has started the season in fine form, already registering three goals in the Serie A. Fellow forward, Insigne also has two goals in Serie A.
With an experienced line-up, including Kalidou Koulibaly at the heart of the defence, Napoli will prove tricky opponents. Liverpool’s front three will have to be at the top of their game if they are to break down Carlo Ancelotti’s formidable side.
Should Liverpool's regular attack of Mohamed Salah, Roberto Firmino and Sadio Mane fail to impress, Klopp could have issues with suitable substitutes and may be forced to try his luck with 19-year-old, Rhian Brewster.
The English striker has been added to Liverpool's 20-man squad following Divok Origi’s ankle injury he sustained against Newcastle United at the weekend.
Other than Brewster’s admission to the squad, there remains no new injuries to Liverpool’s team. Goalkeeper, Alisson will miss this fixture however, is reportedly not far away from returning to the team.
Liverpool: Adrian, Alexander-Arnold, Matip, Van Dijk, Robertson, Fabinho, Wijnaldum, Henderson, Salah, Mane, Firmino