The 41 year-old who made his debut for Australia 20 years ago against Canada in a 1994 FIFA World Cup qualifier, had expressed his interest in playing for the Socceroos at the 2014 edition of the tournament, in Brazil.
Schwarzer is believed to have notified Football Federation Australia (FFA) of his decision on Wednesday morning, just hours before Socceroos coach Ange Postecoglou names his squad.
Fans and team-mates flocked to Twitter in support of Schwarzer, with Tim Cahill leading the tributes.
"Mark Schwarzer a true professional and is one of the all time greats for our game to ever wear a Socceroos jersey," Cahill said.
Mile Sterjovski, who repesented the Socceroos 43 times from 2000-2013 wrote:
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