Electrochemical promotion of CO combustion over Pt/YSZ was investigated under high vacuum conditions. A galvanostatic step was coupled to mass spectrometric gas analysis using an electrochemical mass spectrometric monitoring device. Non-Faradaic electrochemical promotion of catalysis took place at 300 degrees C while only electrochemical oxidation was observed at 400 degrees C. Oxygen evolution measurements revealed that electrochemical promotion is related to the thermodynamically stable PtOx species over the Pt/gas interface. The polarization time and O-2 pressure show strong influence on the relaxation transient upon current interruption. We propose that during anodic polarization, PtOx is first formed at the Pt/YSZ interface. With prolonged polarization time, the formed PtOx either migrates over the Pt/gas interface inducing electrochemical promotion or diffuses into the Pt bulk leading to the oxygen storage. After polarization, the stored O species is released and acts as sacrificial promoter causing the persistent electrochemical promotion effect. (C) 2011 Elsevier B.V. All rights reserved.