Britain are entering a men's squad at this year's Olympics for the first time since 1960 in Rome while it will also be a Games debut for the women's team.
The last time Britain fielded a combined England, Wales, Scotland and Northern Ireland football team was for a qualification game against Bulgaria in 1971 when only amateurs were eligible.
It is hoped the match against Brazil at the Riverside on July 20 will wet the appetite for the Olympic tournament which begins in Cardiff five days later.
"I've learned a great deal about the Olympics since I was given the opportunity to lead this team and I realise just how massive it is going to be for the whole of Britain," said Pearce who is also in temporary charge of the England national side.
"In world football they don't come much bigger than Brazil and it should be a terrific occasion," he added in a statement.
Brazil have won the World Cup five times but have never taken the gold medal at the Olympics, landing silver at Los Angeles in 1984 and in Seoul four years later when the likes of Romario and Bebeto were part of the squad.
This year's team is likely to contain highly-rated Santos striker Neymar.
On the same day Britain's men take on Brazil, the women's team managed by Hope Powell are in action against Sweden at the Riverside.
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