The veteran guided the Selecao to the world title in 2002 and Confederations Cup last year but has opted to step aside after the host nation's collapse this summer
The 65-year-old initially refused to step down after Brazil's failure to win the world title on home soil and said at the weekend that it would be up to the CBF to make a decision on his future.
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The Selecao started the tournament as the big favourites, but failed to live up to the expectations as they had to settle for fourth spot overall.
Brazil beat Croatia in their opening game before they were held to a scoreless draw by Mexico. A win over Cameroon saw them book their ticket for the knockout stages, where they beat Chile after spot-kicks and then Colombia 2-1 in the quarter-finals.
The hosts' dream came to an abrupt end in the semi-finals, though, when they were thrashed 7-1 by Germany and Netherlands only poured more salt in their wounds in the third place playoff with a 3-0 win.
Scolari guided Brazil to 19 victories in 29 games during his second spell in charge, winning the Confederations Cup - also on home soil - in 2013.