The 65-year-old faced heavy criticism for the way that the hosts were humiliated 7-1 by eventual winners Germany in the semi-finals of the tournament, and their disappointing third-place playoff defeat to Netherlands.
Scolari's contract with the Brazilian Football Association was due to expire next month and the Portuguese, who lifted the World Cup as Selecao manager in 2002, has resigned to rule out extending his tenure.
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 [Jose Maria] 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 ex-Chelsea boss led Brazil in 29 games from 2013 to 2014, of which he won 19, drew six and lost four, and oversaw their Confederations Cup glory on home soil the summer after his appointment.