The Serie A powerhouse have named ex- Italy manager the veteran manager to lead the team for the remainder of the campaign.
The experienced coach replaces Igor Tudor, who was let go after the Serie A side's defeat by Lazio last weekend.
Tudor had joined the club in March as Thiago Motta's replacement but exited following a seven-month stint at the end of an eight-match winless run.
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 during Roberto Mancini's tenure.
He helped them qualify for 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, 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 in the midweek 3-1 triumph over Udinese 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, having lost once and drawn twice in their opening three matches.
