A self-assembled monolayer of 2-mercaptobenzothiazole (MBT) was adsorbed on surface enhanced Raman spectroscopy (SERS) active gold and silver surfaces. Oxygen reduction induced ion transport and electrolyte spreading processes along the organic/substrate interface were initialised. Resulting changes of the structural monolayer constitution were then investigated by scanning Kelvin probe (SKP) and a novel in situ SERS setup. SKP profiles of the electrochemical interface potential and the investigation of the ion distribution at the surface by time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that the approach is suited to simulate cathodic delamination processes. Complementary X-ray photoelectron spectroscopy (XPS) studies helped to analyse organic species that were formed during the deterioration of the monolayer. (C) 2010 Elsevier B.V. All rights reserved.