The Old Lady have chosen ex- Italian national team manager Spalletti to lead the team for the rest of the term.
The 66-year-old replaces Igor Tudor, who was dismissed after the Serie A side's defeat by Lazio on Sunday.
Tudor arrived at the club in March to replace Thiago Motta but left after seven months after an eight-game winless streak.
Spalletti guided Napoli to the Serie A crown in 2022-23 before taking charge of Italy, after the team's failure to reach the 2022 World Cup with Mancini at the helm.
Under his guidance, they made it to 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, putting Italy in danger of missing a third straight World Cup.
Spalletti has also managed Inter Milan, Roma and Udinese in Serie A and secured two Russian Premier League titles with Zenit St Petersburg.
Massimo Brambilla served as interim manager for Juventus during the 3-1 victory over Udinese on Wednesday which left them seventh in Serie A - six points behind leaders Napoli after nine games.
Their Champions League campaign sees them in 25th place in the group stage, with one loss and two draws in their first three games.