Earlier mechanistic proposals for the EPOC phenomenon with solid electrolytes mainly emphasized tuning of the local work function of the surface of conductive catalysts by spilled-over species, which are in-situ generated during electrochemical polarization processes. It has been proposed that the spilled-over species can subsequently modulate the chemisorption strength between surface adsorbates (intermediates) and catalyst binding sites, thereby influencing the rate or selectivity of the target reactions significantly. Particularly in the case of oxygen-ion conducting electrolyte systems, for instance, the migrated anionic O species from the solid electrolyte to the metal-gas interface has been suggested as the origin of the corresponding EPOC effects along with the evidence that the migrated charged species on the surface can be identified via in-situ spectroscopic methods. On the other hand, the hypothesis of modification of the local work function to explain the origin of EPOC was recently criticized with a different view that heterogeneous catalysis needs to be explained by more recent concepts such as d-band center theory, rather than the surface work function, which might play a more trivial role in understanding of surface reactions.