Sodium periodate was characterized as a primary chemical oxidant for the catalytic evolution of oxygen at neutral pH using a variety of water-oxidation catalysts. The visible spectra of solutions formed from Cp*Ir(bpy)SO(4) during oxygen-evolution catalysis were measured. NMR spectroscopy suggests that the catalyst remains molecular after several turnovers with sodium periodate. Two of our [Cp*Ir(bis-NHC)][PF(6)](2) complexes, along with other literature catalysts, such as the manganese terpyridyl dimer, Hill's cobalt polyoxometallate, and Meyer's blue dimer, were also tested for activity. Sodium periodate was found to function only for water-oxidation catalysts with low overpotentials. This specificity is attributed to the relatively low oxidizing capability of sodium periodate solutions relative to solutions of other common primary oxidants. Studying oxygen-evolution catalysis by using sodium periodate as a primary oxidant may, therefore, provide preliminary evidence that a given catalyst has a low overpotential.