The match, scheduled for Sunday at 4:00 pm (1900 GMT) in Rio de Janeiro's iconic Maracana stadium, will also feature the likes of current men's national team coach Dorival Junior and women's team defender Tamires.
"We've raised the trophy as world champions, now let's raise the cup of solidarity," said 1994 and 2002 World Cup winner Cafu, in comments carried on news site Globo Esporte.
"I want to invite all Brazilians to support this effort to help our brothers in Rio Grande do Sul," Dorival Junior said in a video released by the Brazilian Football Confederation (CBF).
The southern state is reeling from weeks of unprecedented floods that have killed more than 160 people and left 90 percent of its towns inundated, including the state capital, Porto Alegre.
Tickets for the match will start at around $6, with proceeds from sales and the television broadcast going to charities to help flood victims, said TV network Globo, which is sponsoring the event along with the CBF, Rio city hall and popular football club Flamengo.
