The Old Lady have appointed former Italian national team manager the veteran manager to take the helm 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 arrived at the club in March to replace Thiago Motta but exited following a seven-month stint following a string of eight matches without a victory.
Spalletti guided Napoli to the Serie A crown in 2022-23 prior to assuming the Italy role, which missed out on the 2022 World Cup under former boss Roberto Mancini.
He helped them qualify for Euro 2024 but were eliminated in the round of 16 by Switzerland.
Yet, the Italian FA let Spalletti go in June post a qualifying defeat against Norway, with the Azzurri at risk of missing out on a third consecutive World Cup.
Spalletti has also managed Inter Milan, Roma and Udinese in Serie A 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 moving them to seventh position in the league - trailing leaders Napoli by six points after nine matches.
In the Champions League, they sit 25th in the league phase, after recording one defeat and two ties in the initial three fixtures.
