Juventus have chosen former Azzurri boss the veteran manager as their manager until the end of the season.
The experienced coach replaces his predecessor, who was sacked after the Serie A side's defeat by Lazio last weekend.
The former boss came on board 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 before taking charge of Italy, after the team's failure to reach the 2022 World Cup under former boss Roberto Mancini.
He helped them qualify for Euro 2024 where they were knocked out in the last 16 by Switzerland.
Yet, the Italian FA let Spalletti go in June post a qualifying defeat against Norway, with the Azzurri at risk of missing out on a third consecutive World Cup.
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 - trailing leaders Napoli by six points after nine matches.
They are 25th in the league phase of the Champions League, after recording one defeat and two ties in the initial three fixtures.