Preadsorbed water along with surrounding bulk water significantly modulates the surface electronic structure of TiO(2), switches the adsorption mode of dyes, and promotes dye sensitization of TiO(2) under visible-light irradiation. This opens a door toward facile improvement in the efficiency of photodegradation of dyes and dye-sensitized solar cells under visible-light irradiation without any complicated and expensive surface modulation.