The Serie A powerhouse have chosen previous Italian national team manager the veteran manager to take the helm until the end of the season.
The experienced coach replaces his predecessor, 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 following a string of eight matches without a victory.
Spalletti led Napoli to the Serie A title in 2022-23 then moving on to lead the Italian national team, who had failed to qualify for the 2022 World Cup during Roberto Mancini's tenure.
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 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 secured two Russian Premier League titles with Zenit St Petersburg.
Massimo Brambilla served as interim manager for Juventus in the midweek 3-1 triumph over Udinese placing them seventh in the Serie A standings - six points adrift of Napoli at the top after nine rounds.
Their Champions League campaign sees them in 25th place in the group stage, having lost once and drawn twice in their opening three matches.