We used periodic hybrid-exchange density functional theory calculations to predict the structure of water on the rutile TiO2(110) surface (1 ML), which is an important first step towards understanding the photocatalytic processes that occur in solar water splitting. A detailed model describing the water-water and water-surface interactions is developed by exploring thoroughly the adsorption energetics. The possible adsorption mode—molecular, dissociative, or mixed—and the binding energy are studied as a function of coverage and arrangement, thus separation, of adsorbed species. These dependencies (coverage and arrangement) have a significant influence on the nature of the interactions involved in the H2O-TiO2 system. The importance of both direct intermolecular and surface-mediated interactions between surface species is emphasized. Finally, to gain insight into the photooxidation of adsorbed species at the surface, the electronic structure of the predicted adsorbate-substrate geometries is analyzed in terms of total and projected density of states.