The 64-year-old was officially named as coach at a press conference here Thursday, just six days after the sacking of his predecessor Mano Menezes, reports Xinhua.
"It is important that we make it clear to all Brazilians: Yes, we are obligated to win the World Cup in 2014," said Scolari, who led Brazil to victory at the 2002 World Cup in Japan and South Korea.
"We are playing at home. We are not favourites at the moment but our aim is to become favourites. And a team that has already won the World Cup five times will not settle for second, third or fourth."
As expected, Brazil's 1994 World Cup-winning coach Carlos Alberto Parreira was named as the team's technical assistant.
Scolari revealed 69-year-old Parreira would play an important role in team tactics and selection.
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"I am very happy to have somebody alongside me like Parreira," he said. "It will be important because his ideas are not always the same as mine and he is somebody who I respect a lot. His input will of great benefit to the national team."
Brazil's Football Confederation (CBF) president, Jose Maria Marin,vehemently defended the decision not to appoint a foreign coach amid reports linking the job to former Barcelona boss Pep Guardiola.
"We have to give greater value to what we have in this country, " Marin said. "Our sole commitment is to seek out and offer the best for our football and it is in this vein that we have chosen these two great champions, respected not just in our country but worldwide - Felipe Scolari and Carlos Alberto Parreira."
Calls for Scolari to to be re-appointed had been growing since Brazil's 1-2 loss to Mexico at the final of the London Olympics in August.
Menezes' sacking came despite Brazil's improved recent form, which included victories over Sweden, Japan, Iraq and bitter rivals Argentina.