The 41-year-old Materazzi will be player-manager of the team co-owned by Bollywood actor Abhishek Bachchan, a league spokesman said on Friday.
Materazzi is expected to reach India by Thursday to join a training camp in Bangalore, he added.
The former Inter Milan defender was involved in what is now the lasting impression of the 2006 World Cup which culminated in an eventful final.
Materazzi gave away the penalty which Zinedine Zidane converted to put France ahead before the Italian made amends with the equaliser in the contest in Berlin.
In extra time, Zidane was sent off for headbutting Materazzi, with the France talisman subsequently claiming he was provoked, and Italy went on to win 5-3 on penalties.
Del Piero, Materazzi's team mate in that 2006 squad, has already joined the Delhi franchise in the eight-team league scheduled to run from Oct. 12 to Dec. 20.
Former France and Juventus striker David Trezeguet, compatriot Robert Pires, Spaniards Joan Capdevila and Luis Garcia and former Newcastle United striker Michael Chopra have also confirmed their participation in the league. 

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