The Old Lady have named previous Italian national team head coach the veteran manager to lead the team until the end of the season.
The 66-year-old replaces his predecessor, who was let go after the Serie A side's defeat by Lazio on Sunday.
The former boss came on board in March filling the shoes of Thiago Motta but departed after seven months following a string of eight matches without a victory.
Under Spalletti, Napoli clinched the Serie A championship in 2022-23 before taking charge of Italy, which missed out on the 2022 World Cup under former boss Roberto Mancini.
He secured their spot in Euro 2024 exiting in the last 16 stage against Switzerland.
However, Spalletti was sacked by Italy in June post a qualifying defeat against Norway, with the Azzurri at risk of missing out on a third consecutive World Cup.
Spalletti's managerial career includes Inter Milan, Roma, and Udinese in Serie A and secured two Russian Premier League titles with Zenit St Petersburg.
Massimo Brambilla took interim charge of Juventus in the midweek 3-1 triumph over Udinese moving them to seventh position in the league - six points behind leaders Napoli after nine games.
Their Champions League campaign sees them in 25th place in the group stage, having lost once and drawn twice in their opening three matches.
