Dries Mertens scored both goals - and both in the first half - as the visitors picked up an important win at the Stadio Olimpico.
The Giallorossi, after a slow start, tried to claw their way back into the match in the second half, as Lorenzo Pellegrini went close on a number of occasions.
However, a goal that could have given them a route back into the match proved elusive.
Paulo Fonseca's side now have a two-week wait until their next match due to the international break - they travel to face Sassuolo on April 3.
ROMA 0-2 NAPOLI
SCORERS: Mertens (27', 34')
ROMA (3-4-2-1): Pau Lopez; Mancini, Cristante, Ibanez; Karsdorp, Diawara (Villar), Pellegrini (Kumbulla), Spinazzola; Pedro (Perez), El Shaarawy; Dzeko (Mayoral) ‘
Unused subs: Fuzato, Mirante, Fazio, Reynolds, Santon, Calafiori, Pastore
NAPOLI (4-2-3-1): Ospina; Hysaj, Maksimovic (Manolas), Koulibaly, Mario Rui; Fabian Ruiz, Demme; Politano (Lozano), Zielinski (Elmas), Insigne (Bakayoko); Mertens (Osimhen)
Unused subs: Meret, Contini, Zedadka, Costanzo, Cioffi
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