The Old Lady have named previous Italian national team head coach Spalletti to lead the team for the rest of the term.
The 66-year-old takes over from Igor Tudor, who was let go after the Serie A side's defeat by Lazio last weekend.
The former boss came on board in March filling the shoes of Thiago Motta but exited following a seven-month stint after an eight-game winless streak.
Spalletti led Napoli to the Serie A title in 2022-23 prior to assuming the Italy role, who had failed to qualify for the 2022 World Cup during Roberto Mancini's tenure.
He secured their spot in Euro 2024 but were eliminated in the round of 16 by Switzerland.
Nonetheless, Italy dismissed Spalletti 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 for their 3-1 win against Udinese on Wednesday placing them seventh in the Serie A standings - six points adrift of Napoli at the top after nine rounds.
They are 25th in the league phase of the Champions League, with one loss and two draws in their first three games.