A cylinder head cover structure of an engine includes a positive crankcase ventilation (PCV) valve releasing blow-by gas from an oil separating chamber to an intake system of the engine. The oil separating chamber is included in an oil separator provided to an interior of a cylinder head cover. In the oil separating chamber, oil mist is separated and removed from the blow-by gas. The PCV valve is located between a portion of a defining wall and an exterior wall of the cylinder head cover, and supported by the defining wall and the exterior wall, the defining wall defining the oil separating chamber and the cam housing, and the exterior wall being spaced apart from the portion of the defining wall. The PCV valve is surrounded by a space communicating with the cam housing.