The Serie A powerhouse have appointed ex- Azzurri manager Spalletti to lead the team for the remainder of the campaign.
The 66-year-old steps in for Igor Tudor, who was sacked after the Serie A side's defeat by Lazio on Sunday.
Tudor had joined the club in March filling the shoes of Thiago Motta but left after seven months following a string of eight matches without a victory.
Under Spalletti, Napoli clinched the Serie A championship in 2022-23 prior to assuming the Italy role, who had failed to qualify for the 2022 World Cup under former boss Roberto Mancini.
Under his guidance, they made it to Euro 2024 but were eliminated in the round of 16 by Switzerland.
Nonetheless, Italy dismissed Spalletti in June following a loss to Norway in World Cup qualifying, as Italy faced the possibility of not making a third World Cup in a row.
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 served as interim manager for 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.
In the Champions League, they sit 25th in the league phase, with one loss and two draws in their first three games.
