The Old Lady have named previous Azzurri boss the veteran manager to lead the team for the rest of the term.
The experienced coach replaces his predecessor, who was dismissed 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 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, 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 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, 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 won the Russian Premier League twice with Zenit St Petersburg.
Massimo Brambilla took interim charge of 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, having lost once and drawn twice in their opening three matches.
