The Argentine pope has called for a "cry for peace" from the world's 1.2 billion Catholics, Christians as a whole, believers from other faiths and atheists.
Syria's Sunni Muslim leader, Grand Mufti Ahmad Badreddin Hassoun, has called for Syrians to join in the prayers and the patriarch of Constantinople Bartholomew I, spiritual leader of the world's Orthodox, has said he is also backing the initiative.
There has been a giant mobilisation of Catholic churches worldwide -- through traditional homilies at mass as well as via social media -- for the faithful to pray for peace and engage in some form of fasting.
The four-hour prayer vigil in the Vatican starts at 2230 IST but there will be similar smaller initiatives around the world from Baghdad to Jerusalem, from Mumbai to Buenos Aires, from Washington DC to Beirut.
It has also been compared to impassioned calls for peace by John Paul II in the run-up to the Iraq war and a speech by another papal predecessor, Paul VI, against the Vietnam War at the United Nations.
"This cry from the pope distills the calls coming from the one big family that is humanity," French cardinal Roger Etchegaray, who led peace missions on behalf of John Paul II ahead of the Iraq war in 2003, said.
"Do not be afraid to offer your children a sober meal," he said, adding: "Invite grandparents to a meal that will be poor in nourishment but rich in words."
"If anyone has experienced war, they should talk about what it means to live under a bombardment -- the uncertainty of what tomorrow will bring," Paglia said.
Brazilian cardinal Joao Braz de Aviz, head of the pontifical council overseeing Catholic orders on five continents, said churches and monasteries throughout the world should also take part in the prayers.
