The Arena Corinthians in Sao Paulo will host the tournament’s curtain-raiser in Group A, with Luiz Felipe Scolari’s side strong favourites to lift the trophy for a sixth time.
But Modric is Croatia’s talisman and he is expected to line up in midfield as Nico Kovac’s men look to spoil the party in only their fourth World Cup campaign.
The Real Madrid star has underlined the sense of occasion surrounding the clash and says he expects Brazil to be desperate to kick off the tournament with three points.
"It has been a long while since Croatia played a match as big as this one," he said in The Sun.
"We are all aware of how fired up the Brazilians are to make a winning start on home soil.
"They are a phenomenal team, with Marcelo, Thiago Silva and Neymar the three outstanding players in their team.
"It means we have to breathe as one on the pitch because none of us can put up a one-man show against a team of such quality.
"It will be a titanic tussle in midfield and we are doomed if we surrender possession and try to sit back and defend."
Croatia failed to progress to the knock-out stages of Euro 2012 after being drawn alongside eventual finalists Spain and Italy, but Modric believes that anything is possible this time around with Cameroon and Mexico making up the rest of Group A.
"If we get past the group stage we could go a long way," he said.
"Many Croatian players have improved massively as individuals since Euro 2012 but it is yet to be seen if we have progressed as a team."
Meanwhile, former Arsenal striker Eduardo, who was born in Brazil but has Croatian citizenship and is included in their World Cup squad, admits that there may be split loyalties in his family for the game.
"My family will be at the game and I am not sure who they will be supporting," he said.
"Brazil are the tournament favourites and it will be a big ask for us to beat them. But how well we hold our own could determine our fate in qualifying from our group."