For the production of nonfossil fuels, water oxidation by inexpensive cobalt-based catalysts is of high interest. Films for the electrocatalysis of water oxidation were obtained by oxidative self-assembly (electrodeposition) from aqueous solutions containing, apart from Co, either K, Li or Ca with either a phosphate, acetate or chloride anion. X-ray absorption spectroscopy (XAS) at the Co K-edge revealed clusters of edge-sharing CoO6 octahedra in all films, but the size or structural disorder of the Co-oxido clusters differed. Whereas potassium binding is largely unspecific, CaCo3O4 cubanes, which resemble the CaMn3O4 cubane of the biological catalyst in oxygenic photosynthesis, may form, as suggested by XAS at the Ca K-edge. Cyclic voltammograms in a potassium phosphate buffer at pH 7 revealed that no specific combination of anions and redox-inactive cations is required for catalytic water oxidation. However, the anion type modulates not only the size (or order) of the Co-oxido clusters, but also electrodeposition rates, redox potentials, the capacity for oxidative charging, and catalytic currents. On these grounds, structure–activity relations are discussed.