Electrochemical catalysts based on Pd deposited by Physical Vapour Deposition on YSZ were used for methane deep oxidation. Different thicknesses of Pd films varying from 11 to 75 nm were catalytically characterized between 150 and 750 degrees C. The Pd loadings were extremely low. Catalytic and EPOC experiments were carried out on those electrochemical catalysts. Their catalytic activities were compared with the performances of a reference catalyst. It was found that the catalytic activity can be in situ tuned by applying an anodic polarization thus supplying oxygen ions at the surface of the catalyst. Faradaic efficiency values up to 258 were observed and the induced modifications of the catalytic rate were typically 100 times higher than the corresponding ionic current. The influence of the polarization on the temperature of decomposition of the palladium oxide was also examined. The polarization was found to enhance the thermal stability of the oxide and turn palladium oxide into metallic palladium at higher temperatures.