The electrochemical activation of ethylene oxidation was studied over rhodium catalysts of different thickness (40, 100 and 160 nm) sputtered on top of a thin layer of TiO2 deposited on YSZ. The strong relationship between catalytic activity and oxidation state of rhodium was confirmed. Under open-circuit operation the catalyst potential appears as a suitable indicator of the surface oxidation state of rhodium allowing a prediction of the catalytic behavior from solid electrolyte potentiometric measurements. Under closed-circuit conditions the catalyst potential was used as a tool to tune the catalytic activity of rhodium which showed increasing promotional efficiency with decreasing catalyst film thickness.