The Belgium international beat England goalkeeper Joe Hart three times in nine first-half minutes, seven days after a hat-trick in a 5-0 win over Cagliari.
Mertens drilled his first from a Jose Callejon cut-back and added a penalty before scoring a third from close in.
Torino, 3-0 down after 22 minutes, did fight back in the second half, with Andrea Belotti pulling one back before former Tottenham centre-back Vlad Chiriches added Napoli’s fourth.
Luca Rossettini and Iago Falque, with a penalty, then scored either side of Mertens’ classy effort, but Napoli ensured victory to move up to third.
The last player to score hat-tricks in consecutive Serie A matches was Juventus forward Pietro Anastasi in May 1974.
In Sunday’s early Serie A match, Antonio Candreva’s first-half goal gave Inter Milan a third successive league win, 1-0 at Sassuolo. Stefano Pioli’s side finished with 10 men after Felipe Melo was sent off in stoppage time for two bookable offences.
Bottom club Pescara remain without a league victory after losing 3-0 at home to Bologna, while Crotone stay in the relegation zone after a 2-0 defeat at Udinese. Elsewhere, Chievo beat Sampdoria 2-1.
-BBC
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