Rubber-metal assemblies used for submarine applications are often associated to cathodic protection which can lead to cathodic disboncling of the polymer/metal interface. The degradation mechanisms of polychloroprene/epoxy adhesive/copper-aluminium substrate systems associated to an accelerated ageing test are compared to the degradations resulting from natural ageing conditions in the Mediterranean sea. From destructives tests, a kinetic in four steps is identified for both ageing conditions. This kinetic is confirmed by Electrochemical Impedance Spectroscopy data during ageing. In order to further identify the failure mode, the disbondecl surfaces on polymer and steel sides are analyzed using SEM and FTIR. Both ageing conditions present the same type of degradation which validates the fact that the accelerated ageing protocol reproduces the natural conditions. The chemical transformations in delaminated epoxy are very similar to the chemical transformation in epoxy coatings under high energy electron-beam irradiation. However, bidendate metal carboxylates rather than carboxylic acid chain ends are the main oxidation products due to the alkaline environment at the coating-metal interface. It was shown that the metal/polymer interface is not destroyed by an alkaline attack but by a strongly oxidative attack caused by the intermediates of the oxygen reduction. (C) 2011 Elsevier B.V. All rights reserved.