The Serie A powerhouse have chosen former Azzurri manager Spalletti as their manager for the remainder of the campaign.
The 66-year-old takes over from Igor Tudor, who was dismissed following the loss to Lazio recently.
Tudor arrived at the club in March filling the shoes of Thiago Motta but left 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 with Mancini at the helm.
Under his guidance, they made it to Euro 2024 where they were knocked out in the last 16 by Switzerland.
Nonetheless, Italy dismissed Spalletti 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.
Massimo Brambilla served as interim manager for 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.
In the Champions League, they sit 25th in the league phase, after recording one defeat and two ties in the initial three fixtures.