The relation between the catalyst potential and the catalytic performance has been investigated in the gas-phase combustion of propylene with oxygen over rhodium catalysts at 375 °C. The rhodium catalyst, deposited on yttria-stabilized zirconia (YSZ) solid electrolyte, also served as working electrode in the electrochemical cell. Under open-circuit conditions, the measured catalyst potential was found to be a sensitive indicator of the oxidation state of the rhodium catalyst, which influences the catalytic reaction rate dramatically and depends strongly both on the method of catalyst film preparation and on the composition of the reacting gas mixture. In turn, under closed-circuit conditions, the applied catalyst potential is a convenient tool to maintain the catalyst in its more active, reduced form and to control its catalytic performance. The activity of atomic oxygen at the three-phase boundary (tpb) during open-circuit catalytic reaction was estimated from solid electrolyte potentiometric (SEP) measurements, in good agreement with the average surface oxidation state obtained from XRD and XPS analyses. O/Rh atomic ratios higher than stoichiometric were found by XPS at the outer surface of the catalysts suggesting a strong open circuit O2− spillover due to strong metal support interactions (SMSI) and a concomitant extension of the electric double layer to the gas-exposed catalyst surface, similarly to emersed electrodes in aqueous electrochemistry. Applying potentials up to several hundreds of mV, highly nonfaradaic promotion of propylene combustion was achieved. Electrochemical promotion of catalysis (EPOC) was most efficient at stoichiometric gas composition, that is, close to the limit of surface reduction, and with the catalyst exhibiting the smallest O2− spillover population at open-circuit conditions.