Rafael Benitez's side are six points off the men from the capital, who also hold a game in hand over their hosts this weekend.
The pair have met three times already three times this season, the hosts triumphing on each occasion and Napoli can take confidence from a 3-0 success over Napoli in the Coppa Italia in February.
That win helped Napoli on their route to the Coppa final, where they will face Fiorentina at the end of the season.
There may be focus on the stands as well as the pitch for the game with Roma having been punished for discriminatory chants towards Naples this term.
Juventus host Fiorentina on Sunday in a dress rehearsal for the sides' UEFA Europa League last 16 tie, the first leg of which is at Juventus Stadium on Thursday.
However, the visitors will have their eye on a rare chance to do the double over the league leaders, having triumphed 4-2 in the reverse fixture.
Vincenzo Montella is the only head coach to have taken all three points from Juventus in Serie A this season, but Fiorentina have not beaten the Turin club away from home in the league since 2008.
Two consecutive defeats have seen Torino slip out of the race for fifth place - the final UEFA Europa League qualification spot - but they can claw their way back in when they travel to fifth-placed Inter.
Clarence Seedorf gets the chance to exact revenge on Udinese's Francesco Guidolin at the Stadio Friuli.
The Dutch coach suffered his first loss in charge of Milan to Guidolin in the Coppa Italia and will be keen to take all three points when they travel to Udine on Saturday.
Two sides pushing for a top-five finish, Parma and Verona, meet at the Ennio Tardini on Sunday, while at the bottom, Eusebio Di Francesco prepares for his first game back in charge of Sassuolo against fellow strugglers Bologna.
Sassuolo have not won since Di Francesco left the club in January and they will hope his return following the sacking of Alberto Malesani can help them to inflict a third defeat in four matches on their opponents.
Only goal difference is keeping Chievo out of the bottom three at the expense of Livorno, and both sides face Genoese opposition this weekend.
Chievo will host mid-table Genoa, while Livorno travel to Sampdoria, who ended a run of two-consecutive defeats with a 2-0 win over Torino last weekend.
Elsewhere, Cagliari travel to Siciliy to face second-bottom Catania and Lazio entertain Atalanta at the Stadio Olimpico.
