The Old Lady have chosen former Italian national team boss the veteran manager to lead the team for the remainder of the campaign.
Spalletti takes over from Igor Tudor, who was dismissed following the loss to Lazio on Sunday.
Tudor arrived at the club in March filling the shoes of Thiago Motta but departed after seven months at the end of an eight-match winless run.
Spalletti led Napoli to the Serie A title in 2022-23 then moving on to lead the Italian national team, who had failed to qualify for the 2022 World Cup under former boss Roberto Mancini.
Under his guidance, they made it to Euro 2024 exiting in the last 16 stage against Switzerland.
Nonetheless, Italy dismissed Spalletti in June after a World Cup qualifying defeat by 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 won the Russian Premier League twice with Zenit St Petersburg.
Massimo Brambilla served as interim manager for Juventus in the midweek 3-1 triumph over Udinese placing them seventh in the Serie A standings - six points adrift of Napoli at the top after nine rounds.
They are 25th in the league phase of the Champions League, with one loss and two draws in their first three games.
