The Old Lady have named ex- Italian national team boss the veteran manager to take the helm for the rest of the term.
The experienced coach takes over from the Croatian manager, who was sacked following the loss to Lazio recently.
The former boss came on board in March as Thiago Motta's replacement but exited following a seven-month stint after an eight-game winless streak.
Under Spalletti, Napoli clinched the Serie A championship in 2022-23 prior to assuming the Italy role, which missed out on 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 following a loss to Norway in World Cup qualifying, with the Azzurri at risk of missing out on a third consecutive World Cup.
Spalletti's managerial career includes Inter Milan, Roma, and Udinese in Serie A and lifted the Russian league trophy twice while at Zenit St Petersburg.
Massimo Brambilla took interim charge of Juventus for their 3-1 win against Udinese on Wednesday placing them seventh in the Serie A standings - trailing leaders Napoli by six points after nine matches.
In the Champions League, they sit 25th in the league phase, with one loss and two draws in their first three games.