The mechanism of water photooxidation reaction at atomically flat n-TiO2 (rutile) surfaces was investigated in aqueous solutions of various pH values, using photoluminescence (PL) measurements. The PL bands, which peaked at around 810 and 840 nm for the (1110) and (1100) surfaces, respectively, were assigned to radiative transitions between conduction-band electrons and surface-trapped holes (STH), [Ti-O=Ti-2](s)(+), formed at triply coordinated (normal) 0 atoms at the surface lattice. The PL intensity (/(PL)) decreased stepwise with increasing solution pH, namely, it sharply decreased at around pH 4, near the point of zero charge of TiO2 (about 5), and then rapidly decreased to zero near pH 13. The first sharp decrease around pH 4 is attributed to the increased rate of nucleophilic attack of a water molecule to a hole at a site of surface bridging oxygen (Ti-O-Ti), the density of which increases with increasing pH. The nucleophilic attack is regarded as the main initiating step of the water oxidation reaction in low and intermediate pH. The high PL intensity at low pH is ascribed to slow nucleophilic attack owing to a very low density of Ti-O-Ti by its protonation at the low pH. The second sharp decrease near pH 13 is attributed to formation of surface anionic species like Ti-O- which can be readily oxidized by photogenerated holes. Interrelations between reaction intermediates proposed in this work and those reported by time-resolved laser spectroscopy are discussed.