Photolummescences were observed from vacuum-deposited TiO2 (240 nm set-thick) and SiO2/TiO2 multilayer films with photo-catalytic activities. More intense luminescence was observed from the SiO2 (20 nm set-thick)/TiO2 Multilayer film than from the bare TiO2 film, the former film being known to have higher photo-catalytic activity and photocurrent. The time-resolved photoluminescence upon excitation at 266 nm using a femtosecond pulse laser system showed bi-exponential decays. The two decay lifetimes of the emission from the multilayer film were both found to be longer than those from the bare TiO2 film. This finding indicates the presence of longer-lived photo-generated charge carriers at the SiO2/TiO2 interface, where the nanometer-scale SiO2 overlayer suppresses electron-hole recombination. (C) 2003 Elsevier Science B.V. All reserved.