The Spaniard was his side's hero once more as he and Marek Hamsik struck in the first half to earn the San Paolo side three precious points
Sensational strikes from Jose Callejon and Marek Hamsik proved enough for the San Paolo outfit to claim all three points, although Lucas Castro's tap-in, coupled with the hosts' profligacy, set up a nervy finish.
Partenopei boss Rafael Benitez opted to rotate his squad with an eye on next week's Champions League clash with Olymique de Marseille, and restored Lorenzo Insigne to the side in support of Gonzalo Higuain.
However, it was Callejon who broke the deadlock with a spectacular effort that curled into the top corner of Mariano Andujar's net, taking the Spaniard's tally to six goals in 11 games.
Insigne then combined impeccably with Hamsik to double Napoli's advantage, with the Slovakian powering home a first-time blockbuster, after his team-mate had weaved his way past several Catania defenders.
The home side proceeded to comfortably dominate possession, but Castro's goal and the numerous failures of Higuain and Raul Albiol to find the back of the net from a host of gilt-edged goalscoring opportunities kept Catania in the game.
Nevertheless, Napoli ultimately managed to see off the minnows for the win, prompting Benitez to heap praise on Callejon, who has been in sensational form since joining from Real Madrid during the summer.
"When I said he would score many goals, it is because I know him and am aware of his quality," the coach told reporters after the match.
"He is a guy who works hard and always wants to learn. But all the attackers can play with each other and this means we are expressing our football well.
"I can confirm that we have room for improvement and I repeat: we are only at 75 per cent."
Despite failing to get on the scoresheet, Higuain was happy with his return from injury.
"I am satisfied with how I am recovering," the forward said. "I'm constantly feeling better and am happy with how the squad is playing.
"The league is long and we want to take it game by game. Next Sunday we face Juventus, but there is the important appointment of the Champions League before that and we want to achieve major results."
Napoli remain on an even keel with Borussia Dortmund and Arsenal with six points in Group F, and will be targeting a double victory over Marseille on Wednesday to keep their chances of progressing alive.