The September 17 fixture will pit the Vatican XI against a side of Britain's royal household made up of soldiers, guards and staff. Two days later the Holy See's representatives will play a Church of England team in Canterbury.
It was not clear if the Queen, who visited Pope Francis in April, will attend at Windsor.
"I think Her Majesty and Windsor Castle itself would see this as a golden opportunity for goodwill," said Anglican Archbishop David Moxon, the representative in Rome of the Archbishop of Canterbury, who heads the 80-million-strong worldwide Anglican communion.
The Canterbury match - intended to promote sport as a vehicle for inter-religious dialogue - will be the first top-level sporting event between the two churches that split nearly 500 years ago when England's King Henry VIII broke with Rome.
Archbishop of Canterbury Justin Welby will attend the 20-overs-per-side charity event - the shortest form of the game and lasting about three hours.
The Vatican formed the St. Peter's Cricket Club, a league composed of teams of priests and seminarians, last October and then challenged the Anglicans.
The Rome-based team will field only one Englishman, Father Tony Currer, a right-handed batsman who is the captain. In keeping with cricket's strong colonial-era heritage, the other players are Catholic seminarians or priests from India, Pakistan and Sri Lanka who are studying or working in Rome.
The idea for a Catholic cricket club was the brainchild of John McCarthy, ambassador to the Vatican from Australia - England's oldest and greatest cricket rival.
Whether Pope Francis has since familiarised himself with the sport was unclear.
But he would doubtless appreciate its emphasis on fair play, and his homeland Argentina - whose cricket association celebrated its centenary last year - boasts one of the stronger international teams outside the former British colonies.
(Reporting By Philip Pullella; editing by John Stonestreet)
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