The Old Lady have chosen previous Italy boss Spalletti as their manager until the end of the season.
The 66-year-old steps in for Igor Tudor, who was sacked after the Serie A side's defeat by Lazio on Sunday.
The former boss came on board in March filling the shoes of Thiago Motta but left after seven months at the end of an eight-match winless run.
Spalletti led Napoli to the Serie A title in 2022-23 then moving on to lead the Italian national team, which missed out on the 2022 World Cup under former boss Roberto Mancini.
He secured their spot in Euro 2024 exiting in the last 16 stage against Switzerland.
Yet, the Italian FA let Spalletti go 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 served as interim manager for Juventus in the midweek 3-1 triumph over Udinese moving them to seventh position in the league - trailing leaders Napoli by six points after nine matches.
They are 25th in the league phase of the Champions League, with one loss and two draws in their first three games.
