The Serie A powerhouse have named previous Azzurri boss Spalletti to take the helm until the end of the season.
The 66-year-old steps in for Igor Tudor, who was dismissed post the Lazio setback recently.
Tudor had joined the club in March to replace Thiago Motta but departed after seven months after an eight-game winless streak.
Spalletti guided Napoli to the Serie A crown in 2022-23 before taking charge of Italy, who had failed to qualify for the 2022 World Cup under former boss Roberto Mancini.
He helped them qualify for Euro 2024 exiting in the last 16 stage against Switzerland.
Nonetheless, Italy dismissed Spalletti in June after a World Cup qualifying defeat by Norway, putting Italy in danger of missing a third straight World Cup.
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 in the midweek 3-1 triumph over Udinese placing them seventh in the Serie A standings - six points behind leaders Napoli after nine games.
They are 25th in the league phase of the Champions League, with one loss and two draws in their first three games.