The effect of cobalt doping into a manganese oxide (tetragonal spinel Mn3O4) nanoparticle cocatalyst up to Co/(Co + Mn) = 0.4 (mol/mol) on the activity of photocatalytic water oxidation was studied. Monodisperse ∼10 nm CoyMn1-yO (0 ≤y≤ 0.4) nanoparticles were uniformly loaded onto photocatalysts and converted to CoxMn3-xO4 nanoparticles through calcination. 40 mol% cobalt-doped Mn3O4 nanoparticle-loaded Rh@Cr2O3/SrTiO3 photocatalyst exhibited 1.8 times-higher overall water splitting activity than that with pure Mn3O4 nanoparticles. Investigation on the band structure and electrocatalytic water oxidation activity of CoxMn3-xO4 nanoparticles revealed that the Co doping mainly contributes to the improvement of water oxidation kinetics on the surface of the cocatalyst nanoparticles.