The 39-year-old Italian, who had spells with Renault, Toyota and Jordan among others, will drive for his own TrulliGP team. They replace British squad Drayson, who were named among the original entrants but have now withdrawn, though they will act as a supplier to Trulli's outfit.
“I am pleased that the FIA selected TrulliGP to be part of the FIA Formula E Championship," said Trulli.
"Having gained fantastic experience as a driver in Formula 1, my involvement in the FIA Formula E Championship will certainly be a new challenge, not only as a driver but also as a team owner.
"Competing at the highest level of performance with a clean energy car with the support of Drayson Technologies makes this challenge even more exciting. I am very pleased to be a pioneer of this new Formula E project.”
Trulli, who started 252 grands prix between 1997 and 2011, has not raced competitively since ending a disappointing two-year spell with Caterham ahead of the 2012 campaign. He won his only grand prix in Monaco during the 2004 campaign and recorded an additional 10 podium finishes in F1.
The new Formula E championship will make use of electric-powered single-seaters, competing in major city centres across the globe. The opening round takes place in Beijing on September 13.