It was a much-needed victory for the hosts, who had won one of their opening four matches, but Napoli were made to battle all the way by an Azerbaijani side who put in a battling performance at the Stadio Diego Armando Maradona.
Both sides are on seven points, with Qarabag a provisional 16th in the league phase standings and Napoli 18th.
Qarabag showed their intent from the start, pressing high up the pitch, and Emmanuel Addai came close early on with a powerful low effort from distance that flew just wide.
Napoli managed to get a foothold in the game, but their typical patient build-up play did little to trouble the visitors until a David Neres overhead kick brought a spectacular save from Qarabag keeper Mateusz Kochalski.
Qarabag continued to threaten, with Addai having another shot deflected into the side netting, and a balanced opening half ended goalless.
Visiting striker Camilo Duran tried his luck from a wide angle shortly after the break but Napoli keeper Vanja Milinkovic-Savic managed to hold onto the ball at the second attempt.
Qarabag conceded what looked a rather harsh penalty for what the referee saw as a foul by Marko Jankovic on Giovanni Di Lorenzo but Kochalski went the right way to deny Hojlund with a one-handed save.
Napoli began to stream forward, Kochalski again saving from Neres, and when the keeper stopped Mathias Olivera’s close-range effort, the resulting corner brought the opening goal in the 65th minute.
Kochalski batted away the ball from an attempted clearance by his own defender but McTominay was perfectly placed to head in the rebound.
McTominay’s attempted overhead kick seven minutes later was turned into his own net by Jankovic and the Azerbaijani side had no response as Napoli earned the win on the fifth anniversary of Diego Maradona’s death.
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