The joint session of both chambers of parliament together with regional representatives – making for 1,007 voters in total – will meet at 08:00 GMT, said the statement released on Monday.
There needs to be a two-thirds majority behind a single candidate in the first three rounds of voting, after which a simply majority will suffice.
No single party or coalition holds a simple majority, meaning there will have to be some kind of compromise which analysts hope could be the basis for a broader agreement to establish a new government after two months of deadlock.
Pier Luigi Bersani's centre-left coalition narrowly won the February 24th-25th elections but failed to get enough votes for an overall majority in parliament.
He has failed to woo lawmakers from a new anti-establishment party, the Five Star Movement, and has ruled out a grand coalition with Silvio Berlusconi's centre-right coalition, which came a very close second in the election.
Behind-the-scenes talks between parties in recent days have focused on the presidential vote – seen as a key step since the new president will have the power to dissolve parliament and call early elections if there is no deal.
President Giorgio Napolitano, 87, does not have that constitutional power as he was in the last months of his seven-year mandate.
The Italian presidency is a mostly ceremonial role but it takes on crucial importance during the country's political crises.
Napolitano helped steer the nomination of outgoing Prime Minister Mario Monti after Silvio Berlusconi's ouster in 2011.
Three former prime ministers — Giuliano Amato, Massimo D'Alema and Romano Prodi – are among the names being mentioned as possible successors.
But there are also believed to be "outsider" candidates like Gino Strada, head of the medical charity Emergency, and Emma Bonino, a former European commissioner and human rights activist.