The Serie A powerhouse have appointed former Azzurri head coach Spalletti to take the helm until the end of the season.
The 66-year-old takes over from Igor Tudor, who was let go after the Serie A side's defeat by Lazio last weekend.
Tudor arrived at the club in March as Thiago Motta's replacement 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 during Roberto Mancini's tenure.
He secured their spot in 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, as Italy faced the possibility of not making a third World Cup in a row.
Spalletti has also managed Inter Milan, Roma and Udinese in Serie A and lifted the Russian league trophy twice while at Zenit St Petersburg.
Juventus were temporarily led by Massimo Brambilla in the midweek 3-1 triumph over Udinese which left them seventh in Serie A - six points behind leaders Napoli after nine games.
In the Champions League, they sit 25th in the league phase, after recording one defeat and two ties in the initial three fixtures.