Chicago-born Robert Francis Prevost, who became head of the world's 1.4 billion Catholics on May 8, stood in the white vehicle as it drove through cheering crowds, smiling, waving and making the sign of the cross.
Leo will preside over the ceremony rich in rites and symbols, where he will receive his special papal ring before giving a homily that will set the tone for his papacy.
In meetings with journalists, clergy and diplomats, he repeatedly called for peace in a world full of conflicts and defended social justice.
Inacia Lisboa, 71, originally from Cape Verde but who lives in Rome, said she got up early to get a good spot to see a man she said had already “entered my heart”.
Zelensky, Merz
Before becoming pope, the new pontiff on his personal X account reposted criticism of President Donald Trump's administration over its approach to migration and also pilloried Vance, but the account is no longer accessible.
Other notable guests expected include Ukraine's Volodymyr Zelensky -- who memorably met Trump in St Peter's Basilica at Francis's funeral -- and German Chancellor Friedrich Merz.
Italian authorities have deployed thousands of security officers for the event, alongside snipers on rooftops and anti-drone operations.
Leo XIV was elected the 267th pope on May 8 after a secret conclave vote of cardinals that lasted less than 24 hours.
Modernity is not the concern on Sunday, however.
Leo will begin by visiting the tomb of Saint Peter -- who in the Christian tradition was one of the Twelve Apostles of Jesus Christ, and the first pope -- located under the altar of the basilica that bears his name.
With other cardinals and clergy, the pope will walk in procession into St Peter's Square, where large screens will display the proceedings to the crowds.
At the end of the ceremony, the pope will greet the delegations of heads of state, though it is not clear if any of them will also be accorded a one-to-one private audience.
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