The photocatalytic oxidation of water to molecular oxygen is a key step toward the conversion of solar energy to fuels. Understanding the detailed mechanism and kinetics of this reaction is important for the development of robust catalysts with improved efficiency. TiO2 is one of the best-known photocatalysts as well as a model system for the study of the oxygen evolution reaction (OER). Here we use hybrid density functional based energetic calculations and first-principles molecular dynamics simulations to investigate the pathway and kinetics of the OER on the majority (101) surface of anatase TiO2 in a water environment. Our results show that terminal Ti–OH groups are stable intermediates at the aqueous (101) interface, in accord with the experimental observation that OH radicals are efficiently produced on anatase. Oxidation of Ti–OH gives rise to a second stable intermediate, a surface-bridging peroxo dimer ((O22–)br) composed of one water and one surface lattice oxygen atom, consistent with the surfa...