The Serie A powerhouse have appointed previous Italy head coach the veteran manager to lead the team for the remainder of the campaign.
Spalletti replaces Igor Tudor, who was sacked after the Serie A side's defeat by Lazio last weekend.
Tudor arrived at the club in March to replace Thiago Motta but left after seven months at the end of an eight-match winless run.
Under Spalletti, Napoli clinched the Serie A championship in 2022-23 then moving on to lead the Italian national team, after the team's failure to reach the 2022 World Cup under former boss Roberto Mancini.
He secured their spot in Euro 2024 but were eliminated in the round of 16 by 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 lifted the Russian league trophy twice while at Zenit St Petersburg.
Massimo Brambilla took interim charge of Juventus during the 3-1 victory over Udinese on Wednesday which left them seventh in Serie A - 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.
