This study examined the photoreduction of CO2 to CH4 over TiO2/x mol% Cu-TiO2 double layered films. x mol% Cu-incorporated TiO2 nano-sized powders were prepared using a conventional solvothermal method. The prepared powders were fabricated as TiO2 (bottom)/Cu-TiO2 (top) double layered films for applications to the photoreduction of CO2. The amount of CH4 generated from the photoreduction of CO2 with H2O increased remarkably over the TiO2/Cu-TiO2 double layered films compared to the TiO2/TiO2 double-layered films. In particular, the amount of CH4 gas evolved over the TiO2/5.0 mol% Cu-TiO2 doubled layered film was twice as high as that produced over the TiO2/TiO2 double layered film. A proposed model suggested that the photoactivity over the TiO2/Cu-TiO2 double layered films can be enhanced by effective charge separation and inhibited recombination of the photogenerated electron-hole (e(-)/h(+)) pairs during interfacial transfer between TiO2 and Cu-TiO2. (C) 2015 Elsevier Ltd. All rights reserved.