Scolari, 65, won the tournament in 2002 but the hosts could only finish fourth at this year’s event.
Brazil were thrashed 7-1 by Germany in the semi-finals then lost 3-0 to the Netherlands in the play-off.
“Luiz Felipe Scolari and his fellow coaching staff surrendered their positions to the board,” the CBF confirmed in a statement.
“Scolari and his entire coaching staff deserve our respect and gratitude. They were responsible for returning to the Brazilian people your love for the national team, despite not having achieved our greatest goal.”
Scolari’s contract was set to expire after the tournament, but the CBF vice president Marco Polo del Nero last week offered the manager his full backing following the humiliating last-four defeat by Germany.
However, Scolari himself had offered no assurances about his position in the wake of what he called “the worst day of my life”.
Scolari first took over the Brazil side in 2001 and guided them to World Cup success a year later, beating Germany 2-0 in the 2002 final in Yokohama, Japan.
But after spells in charge of Portugal, Premier League side Chelsea, Bunyodkor of Uzbekistan and Brazilian club Palmeiras, he resumed control of the national team in 2012.
Brazil hosted and won the Confederations Cup in 2013, beating Spain 3-0 in the final, and were favourites to win a sixth World Cup.
They finished top of their group after two wins and a draw from their three matches, before edging past Chile on penalties in the last 16.
They beat Colombia 2-1 in the quarter-finals, but lost top goal-scorer Neymar to a spine injury and captain Thiago Silva to suspension.
In the semi-final, Brazil were 5-0 down to Joachim Low’s Germany after only 29 minutes, before losing 7-1 – their joint-heaviest loss ever and first home competitive defeat for 39 years.