There has been a long-standing controversy as to whether water can dissociate on perfect areas of a TiO2(110) surface; most early theoretical work indicated this dissociation was facile, while experiments indicated little or no dissociation. More recently the consensus of most theoretical calculations is that no dissociation occurs. New results presented here, based on analysis of scanned-energy mode photoelectron diffraction data from the OH component of O 1s photoemission, show the coexistence of molecular water and OH species in both atop (OHt) and bridging (OHbr) sites. OHbr can arise from reaction with oxygen vacancy defect sites (Ovac), but OHt have only been predicted to arise from dissociation on the perfect areas of the surface. The relative concentrations of OHt and OHbr sites arising from these two dissociation mechanisms are found to be fully consistent with the initial concentration Ovac sites, while the associated Ti-O bondlengths of the OHt and OHbr species are found to be 1.85±0.08Å and 1.94±0.07 Å, respectively.