The 10-week inter-city league commencing on October 12, features eight franchises and is the brainchild of the All India Football Federation and its marketing partner IMG-Reliance.
Earlier this month, Spain’s 2010 World Cup winner Joan Capdevila was signed up as one of eight marquee footballers to play in the ISL and 1998 winner Pires is delighted to have joined him.
"I am very happy to be part of the new league when passion for football in India is on the rise,” said the former Marseille and Villarreal winger.
“It will be great to play in front of the enthusiastic Indian fans as well as share all my knowledge with my team-mates. I am sure the League will be a huge success and I am delighted to be part of it.”
Pires, who provided the assist for David Trezeguet’s winning goal against Italy in the Euro 2000 final, will also join his former Arsenal team-mate Freddie Ljungberg in the league.
The pair won two titles together in north London and were part of Arsene Wenger’s ‘Invincibles’ side which went unbeaten in 49 consecutive Premier League matches.
Champions League winner Luis Garcia has also been pencilled in to play in the ISL along with another former Liverpool player David James.
Last month, Premier League chief executive Richard Scudamore confirmed a strategic partnership with the Indian Super League, which is sponsored by motorcycle manufacturer Hero and will be broadcast on the Star India television network.
La Liga champions Atletico Madrid, Serie A side Fiorentina and Dutch Eredivisie outfit Feeyenoord have also entered into alliances with different ISL teams
Co-owners of franchises participating in the league include former India Test captain Sourav Ganguly and the highest run scorer in history Sachin Tendulkar.
Bollywood stars Salman Khan and John Abrahams also hold stakes in different sides.