This study focused on toluene photodecomposition in the presence of H2O over metal (Ba, Al, Si, V, and W)-incorporated TiO2. The nanometer-sized, metal-TiO2 photocatalyst samples, including Ba2+, Al3+, Si4+, V5+, and W6+ ions, were prepared by using the solvothermal method. The X-ray photoelectron spectroscopy (XPS) results showed that the Ti-OH peak, which indicates hydrophilicity, increased with increasing Al and Si ion components but decreased with increasing Ba, V, and W ion components. The contact angles were distributed over the range of 0-10° on almost all films (200-nm thick) after irradiation for 2 h, and in particular approached 0° on the Al-TiO2 and Si-TiO2 nanometer-sized films after just 30 min. The toluene (100 ppm) photodecomposition in the continuous system increased in the order of Al-TiO2>Si-TiO2>pure TiO2>W-TiO2>Ba-TiO2>V-TiO2, and the maximum toluene conversion rate achieved was 45% over Al-TiO2 film after 120 min. The toluene conversion remarkably increased; however, over all photocatalysts, with H2O addition during the toluene photo-decomposed reaction, and in particular, the conversion reached up to 90% after 120 min over Al-TiO2 and Si-TiO2 with increased hydrophilicity. After photoreaction for 24 h, minimal carbon was deposited on the photocatalyst under both reaction conditions, with and without H2O addition, although the deposited carbon amounts were smaller for the former. These results confirmed that the hydrophilicity of the photocatalyst had a greater effect on toluene decomposition, while the photocatalytic deactivation could be retarded by H2O supplementation during toluene decomposition.