The Serie A powerhouse have chosen previous Italy manager Spalletti to lead the team until the end of the season.
The experienced coach replaces Igor Tudor, who was sacked after the Serie A side's defeat by Lazio last weekend.
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 guided Napoli to the Serie A crown in 2022-23 before taking charge of Italy, who had failed to qualify for the 2022 World Cup during Roberto Mancini's tenure.
Under his guidance, they made it to Euro 2024 but were eliminated in the round of 16 by Switzerland.
Yet, the Italian FA let Spalletti go in June post a qualifying defeat against 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 won the Russian Premier League twice 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 - trailing leaders Napoli by six points after nine matches.
They are 25th in the league phase of the Champions League, having lost once and drawn twice in their opening three matches.
