The Serie A powerhouse have named previous Azzurri head coach the veteran manager as their manager for the remainder of the campaign.
The 66-year-old replaces Igor Tudor, who was sacked following the loss to Lazio on Sunday.
The former boss came on board in March filling the shoes of Thiago Motta but exited following a seven-month stint at the end of an eight-match winless run.
Spalletti led Napoli to the Serie A title in 2022-23 before taking charge of Italy, which missed out on the 2022 World Cup during Roberto Mancini's tenure.
Under his guidance, they made it to Euro 2024 exiting in the last 16 stage against Switzerland.
Nonetheless, Italy dismissed Spalletti in June following a loss to Norway in World Cup qualifying, putting Italy in danger of missing a third straight World Cup.
He has previously coached Inter Milan, Roma, and Udinese in Italy's top flight 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 moving them to seventh position in the league - six points adrift of Napoli at the top after nine rounds.
They are 25th in the league phase of the Champions League, having lost once and drawn twice in their opening three matches.
