The defeat no doubt will heap pressure on the German tactician Jurgen Klopp who saw his countryman Thomas Tuchel fired at Chelsea after losing 1-0 to Dinamo Zagreb.
Napoli were quick out of the blocks with Victor Osimhen hitting the post in the second minute and then three minutes later they grabbed the lead when James Milner handled in the box and Piotr Zielinski converted the penalty.
Napoli were opening up Liverpool with ease and were awarded a second penalty. Still, Alisson Becker saved from Osimhen only for the home side to grab a two-goal advantage shortly after thanks to an excellent finish from Andre-Frank Zambo Anguissa.
Substitute Giovanni Simeone made it 3-0 just before the break, slotting home after the outstanding Khvicha Kvaratskhelia had beaten Trent Alexander-Arnold and Joe Gomez and slipped the ball across.
Liverpool replaced Gomez with Joel Matip at the break but within two minutes of the restart, Napoli went 4-0 up as Zielinksi saw his shot blocked by Alisson but reacted sharply to poke the ball home.
Juergen Klopp's side pulled a goal back two minutes later thanks to a fine curling shot from Luis Diaz but there was no way back for the English side
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