Levin has been with Time Warner for 30 years and in the last two years helped orchestrate the biggest media merger of all time between AOL and Time Warner.
Levin is to be succeeded by current co-chief operating officer Richard Parsons, with whom Levin will begin a six-month transition period with immediate effect.
The other co-chief operating officer Robert Pittman becomes sole chief operating officer and chairman Steve Case will continue to work closely with the management team.
Levin said: "After spending virtually all of my career at this great company, it is obviously a major decision for me to begin this succession process. But this is a step that I have been thinking about from some time and whose time has come.
"Given that we are almost a full year into the merger and that an outstanding management team is now in place at the company, I am convinced that AOL Time Warner should begin an orderly transition to a new era of leadership."
AOL Time Warner shares, listed on the New York Stock Exchange, were trading down in early trading by 0.92% at $34.43.
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