Quantum chemical calculations and simulated kinetics were used to examine the structure sensitivity of the oxygen evolution reaction on several surface terminations of Co3O4. Active sites were identified on both the (001) and (311) surfaces consisting of two adjacent Co(IV) cations connected by bridging oxos. Formation of the O-O bond proceeds on these sites by nucleophilic attack of water on a bridging oxo. It was found that the relative turnover frequencies for the different sites are highly dependent on the overpotential, with the dual-Co site on the (311) surface being most active at medium overpotentials where O-O bond formation by water addition is rate limiting. A similar dual-Co site on the (001) surface is most active at low overpotentials where O2 release is rate limiting, and a single-Co site on the (110) surface is most active at overpotentials that are high enough (>0.8 V) to form a significant concentration of highly reactive terminal Co(V)=O species. Two overpotential-dependent Sabatier relationships were identified based on the Brønsted basicity and redox potential of the active site, explaining the change in the active site with overpotential. The (311) dual-Co site that is most active at medium overpotentials is consistent with recent experimental observations suggesting that a defect site is responsible for the observed oxygen evolution activity and that a modest concentration of superoxo intermediates is present on the surface. Importantly, we find that it is essential to consider the kinetics of the water addition and O2 release steps rather than only the thermodynamics.