The 60-year-old, formerly a forward for Cagliari, Napoli, Parma and Chelsea, becomes part of the reshaped Club Italia structure alongside new FIGC president Giovanni Malagò, technical director Claudio Ranieri and head coach Roberto Mancini, completing a leadership team assembled six weeks after Malagò's election.
Zola will retain his position as deputy vice-president of Lega Pro, where he has spent recent years developing the "Zola Reform," a scheme designed to encourage Serie C clubs to give more playing time to young Italian players.
"Zola's charisma, his preparation and his commitment to young players shown in recent years in Lega Pro represent the best foundation to build our future," Malagò said in a statement.
"I thank him because he accepted with enthusiasm, availability and responsibility. With Ranieri, Mancini and Zola, we want to build a new perspective for Italian football."
Zola himself struck a similar tone, framing the appointment as an extension of work already under way in the lower divisions.
"I thank president Malagò for thinking of me for this role," he said. "It's proof of the quality of the project carried out in Lega Pro with the internal structure, with the clubs and with the governance I am part of. I'm putting myself at the disposal of the national team set-up with satisfaction, drive and a sense of duty, aimed above all at the development and growth of new Italian talent."
Despite the new role, Zola will not take up the position of delegation head, which had also been mooted for him; that job would have required him to travel permanently with the senior national team, leaving him unable to continue his Lega Pro commitments.
Malagò and Ranieri are expected to settle that appointment in the coming days, with Gabriele Oriali lined up as team manager and Beppe Bergomi and Bruno Conti among the names under consideration for delegation head, alongside the possibility that Ranieri could initially take on the role himself.
Zola made 35 appearances and scored 10 goals for Italy as a player, and was part of the squad that finished runners-up at the 1994 World Cup, before going on to make his name in England with Chelsea.