Perovskite structured SrTiO3 (STO) was synthesized by a hydrothermal method followed by a second hydrothermal treatment with H2O or NaOH (STO-H2O or STO-NaOH) for the photocatalytic mineralization of gaseous toluene. The second hydrothermal treatment enhances the light absorption and enriches the surface hydroxyl groups of STO. The surface hydroxyls' enrichment of STO promotes the generation of hydroxyl radicals and the separation of photocarriers by the combination of hydroxyl with holes, induces a negative shift of its band edge, and benefits the reduction of adsorbed oxygen. The facile generation of reactive radical species, enhanced light absorption, and improved photocarrier separation together lead to greatly enhanced photocatalytic efficiency of STO-NaOH. Toluene was completely oxidized into CO2 under ultraviolet light illumination for 6 h at room temperature, demonstrating better performance than STO and commercial P25 catalysts. Such a surface hydroxylation promotion strategy may lead to new perceptions of designing an efficient photocatalyst.