The Old Lady have named former Italian national team manager the veteran manager as their manager for the rest of the term.
Spalletti steps in for Igor Tudor, who was let go following the loss to Lazio last weekend.
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 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, as Italy faced the possibility of not making a third World Cup in a row.
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 placing them seventh in the Serie A standings - six points adrift of Napoli at the top after nine rounds.
They are 25th in the league phase of the Champions League, after recording one defeat and two ties in the initial three fixtures.
