The Serie A powerhouse have chosen previous Italian national team boss Luciano Spalletti to lead the team until the end of the season.
The experienced coach replaces Igor Tudor, who was dismissed following the loss to Lazio last weekend.
Tudor arrived at the club in March as Thiago Motta's replacement but left after seven months after an eight-game winless streak.
Under Spalletti, Napoli clinched the Serie A championship in 2022-23 then moving on to lead the Italian national team, who had failed to qualify for the 2022 World Cup under former boss Roberto Mancini.
He secured their spot in Euro 2024 but were eliminated in the round of 16 by Switzerland.
However, Spalletti was sacked by Italy in June post a qualifying defeat against Norway, putting Italy in danger of missing a third straight World Cup.
He has previously coached Inter Milan, Roma, and Udinese in Italy's top flight and secured two Russian Premier League titles with Zenit St Petersburg.
Massimo Brambilla served as interim manager for Juventus in the midweek 3-1 triumph over Udinese which left them seventh in Serie A - trailing leaders Napoli by six points after nine matches.
Their Champions League campaign sees them in 25th place in the group stage, with one loss and two draws in their first three games.