The methodical approach and the cell to study electrochemical processes occurring during cathodic disbondment of a polymer coating are worked out. They permit one to investigate the role of each process separately when supervising the metal substrate potential, electrolyte and polymer coating composition at a metal/polymer/electrolyte interface. The cathodic disbondment of ethylene-vinyl acetate copolymer, polyisoprene and poly(vinyl chloride) coatings are studied. It is found that the cathodic disbondment rate for ethylene-vinyl acetate copolymer coatings depends on double layer parameters at the interface. These parameters are determined by specific volume charge of hydrated cations of the electrolyte, potential of the substrate, the presence of oxygen, surface active substances, etc. Based on the data of IR spectroscopy in internal reflection applied to disbonded films, it is established that during the cathodic disbondment an electron transfer to polymer functional groups, as well as an attacking of the adhesion bonds by active intermediates of oxygen reduction, occurs resulting in an electrochemical degradation of the polymer and an adhesion loss. It is shown that the electrochemical transformations at the steel/poly(vinyl chloride) interface can lead to the appearance of new adhesion bonds, increasing adhesion strength and decelerating the cathodic disbondment.