AZO/TiO2 double-layered semiconductor coupled films were prepared through sequentially depositing AZO and TiO2 films on glass substrates by radio frequency (RF) magnetron sputtering. PVP-pretreatment and post-annealing were performed on these double-layers to achieve an exposure of the AZO buried-layer in different baring conditions. The photocatalytic efficiencies of these buried-layer bared structures were measured through dye decomposition under ultraviolet irradiation. Silver mirror reactions were operated to explore a possible photocatalytic mechanism associated with these buried-layer bared conditions. The buried-layer bared AZO/TiO2 coupled films present 2 ~3 times of photocatalytic activity comparing to the normal AZO/TiO2 double-layered or single layered ones. It suggested that the self-built electrical field formed from coupling semiconductors reduces the recombination of electron-hole pairs, increases the yield of surface photogenerated charges, and enhances the photocatalysis.