Fundamental investigations of the polymer/zinc oxide/zinc interface corrosion stability were performed in situ by means of the electrochemical Height Regulated Scanning Kelvin Probe Blister-Test (HR-SKP-BT) under controlled atmospheric conditions. A hole under an adhesive layer film served as electrolyte reservoir to initiate cathodic de-adhesion processes. Then a combinatorial approach was undertaken to simultaneously study the influence of electrolyte pressure at constant defect polarisation and of relative atmospheric humidity on the de-adhesion rate. The time resolved blister growth and the propagation of the three phase boundary polymer/oxide covered zinc/interfacial electrolyte layer could be detected. It could be proven that the oxygen reduction induced electrochemical damage of the interface precedes the subsequent mechanical de-adhesion process. By variation of the relative atmospheric humidity the water concentration within the bulk adhesive and its interphase adjacent to the metal substrate could be adjusted. These processes were further analysed by peel-tests and in situ Attenuated-Total-Reflection Infrared Spectroscopy (ATR-IR) studies of water diffusion. A decrease of the interphasial water concentration led to a deceleration of the de-adhesion kinetics for constant defect conditions and to smaller interfacial ion transport rates. This could be assigned to an inhibition of the electron transfer reactions at the front of de-adhesion and an increased adhesion force between polymer film and oxide covered metal preventing the formation of an extended interfacial electrolyte layer. (C) 2009 Elsevier Ltd. All rights reserved.