The Serie A powerhouse have named previous Italian national team boss Spalletti to take the helm for the remainder of the campaign.
The experienced coach takes over from Igor Tudor, who was dismissed after the Serie A side's defeat by Lazio on Sunday.
Tudor arrived at the club in March as Thiago Motta's replacement but departed after seven months following a string of eight matches without a victory.
Spalletti guided Napoli to the Serie A crown 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 but were eliminated in the round of 16 by Switzerland.
However, Spalletti was sacked by Italy in June after a World Cup qualifying defeat by 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 secured two Russian Premier League titles with Zenit St Petersburg.
Massimo Brambilla took interim charge of Juventus for their 3-1 win against Udinese on Wednesday which left them seventh in Serie A - six points adrift of Napoli at the top after nine rounds.
In the Champions League, they sit 25th in the league phase, after recording one defeat and two ties in the initial three fixtures.
