Mertens was set up for the opening goal by Marek Hamsik with a clever through ball but still needed to beat the offside trap and two defenders before chipping cleverly over Roma goalkeeper Wojciech Szczesny in the 25th minute.
The Belgian international added a second five minutes into the second half, touching in a cross from the left by Lorenzo Insigne.
But Napoli had to survive an anxious final five minutes after Kevin Strootman pulled a goal back in the 89th minute and Mohamed Salah, who had hit the upright, and Diego Perotti came close to a stoppage-time equaliser with Napoli's Pepe Reina pulling off a dramatic save to ensure the points.
Napoli are now back in contention for an automatic Champions League berth next season as they moved on to 57 points. Second- placed Roma have 59, seven behind leaders Juventus who play at Udinese on Sunday.
RESULTS
Roma 1 (Strootman 89)
Napoli 2 (Mertens 26, 50)
Sampdoria 3 (Fernandes 18, Quagliarella 58, Schick 68)
Pescara 1 (Cerri 32)
Milan 3 (Bacca 24, 70, Lapadula 82-P)
Chievo 1 (De Guzman 43-P)
POINTS TABLE
Teams P W D L GD
Pts
Juventus 26 22 0 4 38
66
Roma 27 19 2 6 33
59
Napoli 27 17 6 4 32
57
Atalanta 26 16 3 7 16
51
Lazio 26 15 5 6 16
50
Milan 27 15 5 7 10
50
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