The present work considers the performance of TiO2-based photosensitive oxide semiconductors as photocatalysts for water purification. This paper brings together the concepts of solid state chemistry for nonstoichiometric compounds and the concepts of photocatalysis in order to discuss the reactivity between TiO2 and water including microorganisms (bacteria and viruses). The performance of TiO2 photocatalysts are considered in terms of a model of photoelectrochemical cell. The experimental data on photocatalytic removal of microorganisms from water are considered in terms of the effect of several properties, including pH, dispersion, light intensity, and temperature. It is argued that correct understanding of the performance of TiO2 photocatalysts requires recognition that properties of TiO2, which is a nonstoichiometric compound, are determined by defect disorder and the related ability to donate or accept electrons. The photocatalytic properties of TiO2 are considered in terms of the reactivity of both anodic and cathodic sites with water and the related charge transfer at the TiO2/H2O interface. It is shown that the formation of well defined photocatalysts requires knowledge of mass and charge transfer during processing and performance, respectively. The main hurdles in the development of high-performance photocatalysts are discussed.