The Frenchman made the announcement after the African side were eliminated from the World Cup following three straight defeats.
"We have lost all three matches and my contract with Cameroon is coming to an end," he told a press conference after his team's 2-1 defeat to the Netherlands at the Green Point Stadium.
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"It was planned all along that I would stop and I will stop with Cameroon."
Le Guen, who took the Cameroon reins in July 2009, has been linked with the head coaching role of the Australian national side but said that he has not yet made any decisions about his future.
"I'm going to think about the future and we will see," he said.
Australian media have said the 46-year-old, a former coach of Paris Saint-Germain, Lyon and Rangers, was the front-runner to succeed Pim Verbeek, who himself has stepped down after Australia were eliminated.
If he is appointed, it would end a run of Dutch coaches in charge of the Socceroos.
Verbeek's replacement could be in charge for Australia's first post-World Cup outing, a friendly in Slovenia in August.
Le Guen was a forlorn figure after Cameroon's defeat to the Netherlands, and accepted full responsibility for their disastrous World Cup.
"I cannot see tonight as any sort of success as we lost the game," he said.
"Maybe we lacked unity and I didn't succeed in unifying the team. The coach is the one who has to take full responsibility and I'm doing it clearly.
"I tried. I thought we had a good mix of experience and youth but we did not get the expected results. I'm not going to point fingers or accuse anybody though."
