KPN is currently the target of a takeover attempt by Mexican billionaire Carlos Slim's company America Movil that values KPN at 10.5 billion euros ($13.5 billion). Movil already owns around 30 percent of the Dutch firm.
KPN said Monday Eric Hageman's decision was "not related to working relationships or present circumstances at KPN."
Hageman, 43, took the job in September 2012.
The company said he had made an "important contribution" to helping the struggling company raise 3 billion euros in a rights issue this spring, and in striking a deal in July to sell KPN's German arm E-Plus to Spanish firm Telefonica.
That move prompted Movil's takeover attempt, which some see as hostile.
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