The Juventus legend has performed a similar ambassadorial role for the Australian A-League, where he scored 24 goals in 48 appearances during a two-year stint with Sydney FC which ended in April.
Del Piero said in a statement: "I am very enthusiastic about this new adventure, it fits perfectly well with the way in which I chose to move forward since I left Juventus, three summers ago.
"I've never wanted repeat the paths I've already walked, I have never looked for emotions that I've already experienced, those are unique and will remain unique and special forever."
"For me, the pitch isn't the only thing that counts, that what surrounds the game counts just as much.
“Above all what is important is the possibility to join together the professional aspect and the role of football ambassador - a chance to proudly represent in the world this wonderful sport, that has become a fundamental part of my life since the day I was born."
After beginning his career with Padova, Del Piero moved to Juventus in 1993 where he scored 290 goals in 705 games during his 19-year stay with the Bianconeri.
A Serie A title winner with Turin-based side on multiple occasions, Del Piero has also won the Champions League, UEFA Super Cup and Intercontinental Cup with Juventus.
The 39-year-old remains the Juventus’ leading goalscorer and also holds the record for the highest number of appearances for the club.
In the eight-team league in India, Del Piero will be reunited with former Juventus strike partner David Trezeguet who has been signed up as the marquee player for FC Pune City.
Earlier this week, Trezeguet told Sky Sports he would be delighted to share their old memories of playing together.
Former Arsenal ‘Invincibles’ Robert Pires and Freddie Ljunberg will also play in the league, as will Spanish duo Luis Garcia and Josemi who won the Champions League in 2005 with Liverpool.
Ex-England goalkeeper David James will be player-manager for the Kerala Blasters franchise, who have also recruited former Newcastle striker Michael Chopra, and are co-owned by Indian cricket legend Sachin Tendulkar.
European sides Atletico Madrid, Inter Milan, Fiorentina and Feyenoord have all entered into technical partnerships with various ISL sides.
The ISL will run from October 12 till December 20.