The Great Britain men's football team will face Brazil in Middlesbrough on 20 July in their only warm-up match for the London Olympics.
Team GB women will entertain Sweden beforehand as part of a double-header at the Riverside Stadium.
"In world football they don't come much bigger than Brazil and it should be a terrific occasion for us," said men's coach Stuart Pearce.
BBC Sport has learned that Neymar is likely to make the Brazil squad.
It is also understood that the senior players on the list for possible selection include Ronaldinho, Chelsea defender David Luiz and Barcelona full-back Dani Alves.
However, Real Madrid's Kaka and AC Milan's Robinho are not in line for selection.
Brazil will announce their final squad during the first week of July.
The game will be the only chance for fans to see the men's and women's teams play before the Olympic football tournament begins five days later when Team GB women take on New Zealand at the Millennium Stadium in Cardiff.
"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 an event it is going to be for the whole of Great Britain," added Pearce.
"Middlesbrough recently hosted an under-21 game and had a tremendous crowd, and I think particularly with the Brazilian connections on Teesside it will be a terrific turnout again come July."
Women's coach Hope Powell said the match against Sweden is a "key part" of their build-up to the Olympics.
"Sweden are a strong side and we want that challenge to be ready for 25 July when the Olympics begins for us," she added.
It will be the first time a Great British Olympic football team has taken to the field in the men's game since 1971 and the first occasion ever for the women's side.