The Old Lady have named ex- Italian national team head coach the veteran manager as their manager until the end of the season.
Spalletti takes over from Igor Tudor, who was dismissed after the Serie A side's defeat by Lazio on Sunday.
Tudor had joined the club in March to replace Thiago Motta but left after seven months following a string of eight matches without a victory.
Spalletti led Napoli to the Serie A title in 2022-23 prior to assuming the Italy role, after the team's failure to reach the 2022 World Cup under former boss Roberto Mancini.
Under his guidance, they made it to 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 during the 3-1 victory over Udinese on Wednesday which left them seventh in Serie A - six points behind leaders Napoli after nine games.
They are 25th in the league phase of the Champions League, after recording one defeat and two ties in the initial three fixtures.
