Abstract It was found that the catalytic activity and selectivity of polycrystalline Ag for the dehydrogenation and decomposition of CH 3OH can be markedly affected by electrochemically pumping oxygen anions from the catalyst surface via stabilized zirconia solid electrolyte cells. The steady-state increases in catalytic rates are typically a factor of 20 higher than the rate of O 2− transfer from the catalyst surface. Oxygen anion pumping causes up to sixfold increases in the rates of production of H 2CO, CO, and CH 4 and induces significant changes in product selectivity. Over a wide range of conditions the rates of the catalytic reactions increase exponentially with catalyst-solid electrolyte interface overpotential η, which is proportional to the induced change in catalyst work function. The phenomena are reversible and show that catalyst work function and catalytic activity and selectivity can be varied deliberately by adjusting the catalyst potential. The observed non-Faradaic rate enhancement for this catalytic system can be interpreted by taking into account the decrease in catalyst work function with decreasing catalyst potential and the consequent changes in the strength of chemisorptive bonds.