Scolari was at the helm 11 years ago as the Ronaldinho-inspired A Selecao became world champions for the fifth time at Korea/Japan 2002.
The pair have been drafted in once more as Brazil go in search of a record sixth FIFA World Cup win on home turf next summer.
"It had not been in my plans," the Atletico Mineiro attacking midfielder said.
"I had a very good season last year so I was hoping it would happen to a certain extent. I am very glad it has come true now.
"There is great pedigree amongst our team. I think we have all the possibilities to win the World Cup.
"We have a mix of young players and experienced players. I am the most experienced player in this team so I will do everything to help my team to win this big aim, which is the World Cup."
Scolari seeking to settle side
Scolari echoed those sentiments ahead of the first game of his second spell in charge of Brazil, adding: "In 2013 we will have 12 or 13 games. It's important we get settled now.
"We want fans to get fascinated about our big goal, which is to be champions in 2014."
David Luiz will have a test on his calf injury before Scolari decides whether he plays although the Chelsea defender has been announced as the team's captain.