Kickoff will be at 8.45pm CET next Monday at Rome's Olympic stadium, but the 77-year-old pope will not be cheering from the stands, despite being an avid football supporter himself.
Nor will he catch it on the big screen, according to a Vatican official, though he is expected to meet with all the players before the match.
Players on the match list include Argentina's Lionel Messi, Italy's Gianluigi Buffon, Cameroon's Samuel Eto'o and Israel's Yossi Benayoun.
Former stars will also dust off their boots for the game, from Italy's Roberto Baggio, to the Ukraine's Andriy Shevchencko and Chile's Ivan Zamorano.
Former Inter Milan captain Javier Zanetti, who is organising the event, told journalists the idea had first been discussed during a private audience he had with the pope in 2013, shortly after Francis's election.
"It's the pope's initiative and a new challenge for peace," said Zanetti, a fervent Catholic known for his charity work.
At half-time the Argentine teenage heartthrob Tini Stoessel will sing John Lennon's "Imagine".
The match is being sponsored by Fiat and Pirelli among others, and viewers will be able to donate money by text message - with funds collected going to a project which supports poor children in Buenos Aires.