The Old Lady have named former Azzurri head coach the veteran manager to lead the team until the end of the season.
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 as Thiago Motta's replacement but left after seven months after an eight-game winless streak.
Under Spalletti, Napoli clinched the Serie A championship in 2022-23 before taking charge of Italy, after the team's failure to reach the 2022 World Cup with Mancini at the helm.
He secured their spot in Euro 2024 exiting in the last 16 stage against Switzerland.
Nonetheless, Italy dismissed Spalletti in June following a loss to Norway in World Cup qualifying, with the Azzurri at risk of missing out on a third consecutive World Cup.
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 during the 3-1 victory over Udinese on Wednesday moving them to seventh position in the league - trailing leaders Napoli by six points after nine matches.
Their Champions League campaign sees them in 25th place in the group stage, with one loss and two draws in their first three games.
