The 65-year-old stood down as the World Cup hosts could only finish fourth, having been thrashed in their semi-final 7-1 by Germany, who went on to lift the trophy in Rio with victory over Argentina, and then beaten 3-0 by Holland on Saturday.
The decision was formally announced on Monday night on the Brazilian Football Confederation website, www.cbf.com.br, following a meeting between Scolari and president Jose Maria Marin, who is scheduled to step down next year in favour of Marco Polo Del Nero.
Only last week Del Nero had given Scolari, who guided Brazil to their fifth World Cup success in 2002, his full backing following the humiliating defeat in Belo Horizonte, which the one-time Chelsea boss described as the "worst day" of his life.
However, it now appears all parties have agreed a fresh approach is needed to rebuild Brazilian football, with Scolari's current contract, which expired at the end of the World Cup, not to be renewed.
A statement from the CBF read: "Coach Luiz Felipe Scolari and his fellow coaching staff surrendered their positions to the board of the Brazilian Football Confederation. The resignation was accepted by president Marin, who was keen to thank all the coaches and players and, by extension, the Brazilian fans for their support throughout the World Cup campaign.
"Scolari and his entire coaching staff deserve our respect and gratitude. They were responsible for returning to the Brazilian people your love for the team, despite not having achieved our greatest goal."
The statement added that Scolari had restored pride to the Brazilian flag and that Marin would give a media conference to expand further.
The 2014 World Cup was the first time in some 39 years Brazil had tasted defeat in a competitive fixture at home, having lifted the Confederations Cup 12 months ago.
The loss of star man Neymar through a back injury in the quarter-final win over Colombia proved key, as Brazil were unable to lift themselves without their talisman, and also suspended captain Thiago Silva, as Germany raced 5-0 ahead inside 30 disastrous minutes at the Estadio Mineirao.
Scolari became the subject of the Brazil fans' frustrations during the Holland game in Brasilia, when his picture on the big screen was met by loud jeers.
There had been so much optimism earlier in the tournament when Brazil had qualified for the knock-out stages top of their group, with two wins from the opening three matches.
However, they needed a nerve-shredding penalty shoot-out to edge past Chile into the quarter-finals.
The hosts had looked more composed as they saw off Colombia 2-1 in Fortaleza, only to then completely fall apart against the rampant Germans and fail to redeem themselves when beaten by the Dutch.
What lies ahead for Scolari is now unclear, the former Portugal manager having also been in charge at Bunyodkor of Uzbekistan and Brazilian club Palmeiras before returning to take over the national team two years ago.
Scolari, however, knows how history will now view him.
"I will be remembered as the coach to lose 7-1, but I knew that risk when I took the job," he said last week.
"The person who decided the line-up, the tactics, was me. It was my choice."
Brazil, meanwhile, will take their time before appointing a permanent successor, with under-23 coach Alexandre Gallo reportedly likely to be the interim caretaker.
Among those expected to be in contention for the full-time job include former Corinthians boss Tite and Muricy Ramalho of Sao Paulo as well as former Brazil boss Vanderlei Luxemburgo.
Brazil have never appointed a foreign coach, although Spaniard Pep Guardiola was linked with the position before he took charge at Bayern Munich.
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