The now-retired 42-year-old tasted success on football's grandest stage when the Selecao won in South Korea and Japan in 2002 with a Luiz Felipe Scolari-led team that also boasted the likes of stars Ronaldo and Ronaldinho.
With his nation now hosting the World Cup, Rivaldo – who scored 34 times in 74 appearances for his country between 1993 and 2003 – has confessed that he does not feel Scolari's current crop rank among the favourites.
“Spain and Argentina are the two strongest teams at the moment," the former Ballon d'Or winner told Goal.
"As we know there are eight world champions who are involved in this tournament, and with all of their experiences, they have all got my respect.
“But Portugal potentially could make an upset.”
On his compatriots' chances, Rivaldo would only go so far as to say that he feels that they will kick off their campaign by beating Croatia in the tournament opener on June 12.
“I think Brazil will do their best," he mused. "I know there will be a pressure before the first game.
"With all my respect, I’m confident we will play a good game and take a victory over Croatia.”
The hosts will be under huge expectations to win their record sixth World Cup title on home soil.
However, the preparations to the tournament in the country have been marred by delays to stadium work and protests over how much the government has spent to stage the competition.
However, Rivaldo does not think that visiting fans should be worried about their safety in Brazil.
“Security will not be a major concern during the World Cup because the governments and organisation committees will ensure that all of conditions will be fine,” he said.
“I hope we could be a good host, because it would be embarrassing for Brazilians if something happened.”