Self-standing porous silica thin films with different pore structures were synthesized by a solvent evaporation method and used as photocatalysts for the photocatalytic reduction of CO2 with H2O at 323 K. UV irradiation of these Ti-containing porous silica thin films in the presence of CO2 and H2O led to the formation of CH4 and CH3OH as well as CO and O-2 as minor products. Such thin films having hexagonal pore structure exhibited higher photocatalytic reactivity than the Ti-MCM-41 powder catalyst even with the same pore structure. From FTIR investigations, it was found that these Ti-containing porous silica thin films had different concentrations of surface OH groups and showed different adsorption properties for the H2O molecules toward the catalyst surface. Furthermore, the concentration of the surface OH groups was found to play a role in the selectivity for the formation of CH3OH.