Corrosion driven delamination of coatings is crucially determined by the rate of the cathodic oxygen reduction reaction at the buried metal-organic coating interface. Quantitative measurement of this rate at such interfaces by conventional techniques is impeded due to the blocking of ion transport by the coating. A new approach where hydrogen permeation is used as a tool to measure the oxygen reduction rate underneath coatings has been recently introduced. This permeation based potentiometry approach measures the rate of the oxygen reduction reaction by correlating the open circuit potential established as a consequence of the dynamic electrochemical equilibrium between hydrogen oxidation and oxygen reduction reactions on the coated exit side with the hydrogen uptake rate on the entry side. In this work, the interfacial reaction kinetics of the oxygen reduction reaction causing delamination of the coating are investigated by this hydrogen permeation based potentiometric approach. Moreover, thus performed prolonged cathodic polarizations of the palladium/coating interface have been found to destroy the interface, just like it is the case in the cathodic delamination process. Initial results obtained on ultra-thin films of iron on palladium are also presented, showing that the technique is applicable also on technically more relevant metal surfaces. (C) The Author(s) 2016. Published by ECS. All rights reserved.