The chemical and electronic properties of passive films on a ZnMg alloy coating can strongly influence the cathodic de‐adhesion process of an applied polymeric coating. Chemical composition of the atmospheric passive film on MgZn2 was compared to the surface state after sequences of Ar/H2 and oxygen plasma treatments by means of in situ IRRAS and ex situ XPS. It could be shown that the chemical composition of the passive film and its electronic properties as displayed by its work function could be significantly changed by the applied plasma processes. As analyzed by Kelvin probe measurements the surface potential could be shifted cathodically by the reductive plasma and anodically by the oxidative plasma. The very negative potentials led to polymer/oxide/metal interface potential more negative than the free corrosion potential of MgZn2. Thereby, a cathodic de‐adhesion process could be perfectly inhibited.