The former Real Madrid, Juventus, Inter and Napoli defender, who also captained Italy to their World Cup triumph in 2006, has been managing Chinese Super League club Guangzhou Evergrande since November 2017.
Cannavaro won the Chinese Super Cup with the club last season, his first trophy as a head coach, but missed out on the title by five points, finishing second behind Shanghai SIPG.
He had managed the club once before for seven months between 2014 and 2015, before spells at Al-Nassr and Tianjin Tianhai.
However, has now taken his first steps into international management, taking charge of the nation in which he has spent the majority of his career as a coach.
China are looking to improve on their disappointing tournament record, with an AFC Asian Cup final and a World Cup group-stage exit in 2002 the highlights, having been knocked out in the quarter-finals of the former tournament this year by Iran as Qatar eventually lifted the trophy.
The length of Cannavaro's deal with the national side is unclear, with the primary focus appearing to be the upcoming China Cup, a competition that includes Thailand - who China face on March 21 - as well as Uzbekistan and Uruguay. The winners will contest the final on March 25.
He has replaced former Italy boss Marcello Lippi, who himself has been retained as an advisor, suggesting a final call on Cannavaro's suitability as permanent manager is yet to be made.
This is the third edition of the China Cup, with Chile, Iceland and Croatia participating in 2017, while Uruguay, Wales and the Czech Republic joined last year. China failed to reach the final both times, finishing third and then fourth.
China will certainly hope a player that has won the Ballon d'Or as a defender, the World Cup at international level, as well as the Under-21 Euros, twice, can help them make the step up. He boasts a glittering trophy cabinet at club level, too, having won La Liga twice with Real Madrid, the UEFA Cup and two Coppa Italias with Parma, among others.