Verbeek, who took charge in December 2007, guided Australia to the World Cup and next year's Asian Cup finals losing only four of his 27 matches in charge.
"It has been a very difficult decision for me after more than two years but it is time for me to look for a new challenge," Verbeek, 54, said in a Football Federation Australia (FFA) release.
"It is a good time to make this announcement so we can now focus completely on preparing everything perfectly for the upcoming World Cup in South Africa," said the Dutchman, who led Australia to their highest FIFA ranking of 14 in September.
Australia have been grouped with Germany, Serbia and Ghana in Group D for the June 11-July 11 World Cup finals in South Africa.
"Pim has done a great job leading the Socceroos and has achieved the best results possible," FFA CEO Ben Buckley said in the statement.
"We will be sad to see him move on after the 2010 FIFA World Cup in South Africa and wish him all the best for the future and he can be proud of what he has achieved."
Verbeek, who was assistant coach with South Korea during the 2002 and 2006 World Cups, did not say if he had another job lined up.
Media reports in Australia suggested that the FFA could appoint a temporary coach ahead of the Asian Cup finals in Qatar in January with a permanent successor in place for the start of the 2014 World Cup qualifying campaign.
"There are processes and planning in place to secure a successor for Pim and we will step up those activities now that it is clear that Pim will not be with us after South Africa," Buckley said.
