The Serie A powerhouse have named previous Italian national team head coach the veteran manager to take the helm for the rest of the term.
The 66-year-old steps in for Igor Tudor, who was dismissed following the loss to Lazio on Sunday.
The former boss came on board in March filling the shoes of Thiago Motta but left after seven months after an eight-game winless streak.
Spalletti led Napoli to the Serie A title in 2022-23 then moving on to lead the Italian national team, which missed out on the 2022 World Cup under former boss Roberto Mancini.
He secured their spot in Euro 2024 where they were knocked out in the last 16 by Switzerland.
Yet, the Italian FA let Spalletti go in June after a World Cup qualifying defeat by Norway, as Italy faced the possibility of not making a third World Cup in a row.
Spalletti's managerial career includes Inter Milan, Roma, and Udinese in Serie A and lifted the Russian league trophy twice while at 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 - six points adrift of Napoli at the top after nine rounds.
They are 25th in the league phase of the Champions League, after recording one defeat and two ties in the initial three fixtures.