Transition-metal oxide and phosphate materials, commonly used for lithium battery devices, are active as oxygen evolution reaction (OER) catalysts under alkaline and neutral solution conditions. Electrodes composed of LiCoO2 and LiCoPO4 exhibit progressive deactivation and activation for OER catalysis, respectively, upon potential cycling at neutral pH. The deactivation of LiCoO2 and activation of LiCoPO4 are coincident with changes in surface morphology and composition giving rise to spinel-like and amorphous surface structures, respectively. The amorphous surface structure of the activated LiCoPO4 is compositionally similar to that obtained from the electrodeposition of cobalt oxide materials from phosphate-buffered electrolyte solutions. These results highlight the importance of a combined structural and electrochemical analysis of the materials surface when assessing the true nature of the OER catalyst.