A World Cup qualifier in 2000 was the last time La Roja defeated the Selecao but, having already ousted Spain from the tournament, they could spring another surprise
The Selecao are unbeaten against their South American rivals since a World Cup qualifier in 2000 and have won 10 of their last 12 meetings with La Roja, but face a Chile side who have already sent Spain packing in this competition.
Brazil boss Luis Felipe Solari said when the original World Cup draw was made that he hoped Chile would be knocked out in the group stages as did not fancy facing the South American side in the second round, a comment which raised eyebrows given the alternatives were 2010 winners Spain and finalists Netherlands.
But Jorge Sampaoli's side advance after beating both Australia and Spain, before losing the Group B decider to the Dutch in their last match.
Brazil, meanwhile, topped Group A after wins over Croatia and Cameroon, plus a goalless draw against Mexico.
The two teams meet for a place in the last eight against either Colombia or Uruguay, meaning there will definitely be at least one South American side in the semi-finals.
Chile reached the last four on home soil in 1962 in what was their only appearance beyond the last 16, but saw that run ended by eventual winners Brazil in a 4-2 loss.
The Selecao have also knocked out Chile in their previous two second-round appearances: a 4-1 win in 1998 and a 3-0 success in 2010.
Four Brazil players, including Neymar and Thiago Silva, have been booked in this tournament and are just one yellow card away from suspension, while Fernandinho is set to replace Paulinho in the hosts' midfield on Saturday.
For Chile, Gary Medel and Arturo Vidal missed training on Thursday afternoon, but both are expected to be fit for Saturday's game.