The Old Lady have chosen ex- Italy boss the veteran manager to take the helm until the end of the season.
Spalletti steps in for his predecessor, who was dismissed post the Lazio setback recently.
The former boss came on board in March filling the shoes of Thiago Motta but exited following a seven-month stint after an eight-game winless streak.
Spalletti guided Napoli to the Serie A crown in 2022-23 then moving on to lead the Italian national team, who had failed to qualify for the 2022 World Cup under former boss Roberto Mancini.
He secured their spot in 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.
Spalletti's managerial career includes Inter Milan, Roma, and Udinese in Serie A 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 - six points adrift of Napoli at the top after nine rounds.
In the Champions League, they sit 25th in the league phase, after recording one defeat and two ties in the initial three fixtures.