The origin of the electrochemical promotion of catalysis (EPOC) was investigated via oxygen temperature-programmed desorption (O2-TPD) from a polycrystalline Pt film interfaced with YSZ. TPD experiments were carried out under operating conditions similar to those used for catalytic activity measurements. This study has clearly shown that an anodic current generates the migration of ‘‘backspillover’’ ionic oxygen species from YSZ toward the Pt surface. These ionic species act as promoters and enable the formation of weakly adsorbed oxygen species coming from the gas phase which are more reactive and thus responsible for the activity enhancement. The effect of polarization is to carry or to remove the promoting ionic species on the Pt surface. Therefore, electrochemical promotion of catalysis can be considered as an electrically controlled metal support interaction, where the support is an O2- conducting solid electrolyte.