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Napoli, with 25 points from 11 games, move three points behind champions Juventus who host Cagliari on Saturday with Inter Milan a further three points back before their game against Genoa.
Lorenzo Insigne opened the scoring for the hosts after nine minutes in the San Paolo Stadium with Belgian Mertens also scoring in the first half.
Mertens added two more after the break in the 64th minute and in stoppage time with Poland’s Arkadiusz Milik also getting on the scoresheet in the last minute.
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Francesco Caputo, who scored the opener against Juventus last weekend, pulled a goal back for Empoli, but it failed to spark a revival for the Tuscan side who remain winless since their the opening match of the season against Cagliari.
Ancelotti rotated his squad ahead of Wednesday’s game against the French champions, bringing in French defender Kevin Malcuit and young midfielders Amadou Diawara and Marko Rog, but he stuck with the trusted forward attack of Insigne and Mertens.
Insigne got the first after nine minutes after good work by Kalidou Koulibaly with the Senegalese defender breaking through from his own half.
Luca Antonelli thought he had scored the equaliser for Empoli on 15 minutes but the goal was ruled offside.
Insigne then intercepted a reckless Giovanni Di Lorenzo back-pass to set up Mertens, who slotted in a low drive from a distance on 38 minutes.
Caputo gave Empoli hope when he beat the offside trap with a diagonal shot after 58 minutes, but six minutes later Mertens got his second.
Insigne and Mertens were instrumental in Milik’s fourth on 90 minutes, with Insigne then setting up Mertens for his 75th Serie A goal deep into injury time.