Traditional oxygen electrocatalysts do not dissociatively chemisorb oxygen, resulting in electrochemical irreversibility. The joint pseudo‐splitting/peroxide mechanism suggests that the main requirement is for the oxygen molecule to be chemisorbed side on: O‐O. This condition will be satisfied by paramagnetic oxides, such as high surface area lithiated nickel oxide and perovskite oxide. Such electrodes exhibit steady and reproducible open‐circuit potentials which are very near the theoretical values and the variation with oxygen partial pressure follows the Nernst equation for a four‐electron process. The current density at constant polarization is directly proportional to the square root of oxygen partial pressure. Homomolecular oxygen studies confirmed that oxygen is dissociatively chemisorbed on such oxides and there is a good correlation between the activation energies for the isotopic exchange and electrochemical reduction of oxygen, suggesting a similar mechanism is involved in each case.