A novel tri-layer film photoelectrode structure of DSSC by introducing Eu3+ and Er3+ ions into TiO2 film was proposed. The photoelectric conversion efficiency of the DSSC with Er3+:TiO2/Eu3+:TiO2/TiO2 tri-layer electrode reaches 7.41%, increased by a factor of 1.44 compared to that of the DSSC without Eu3+ and Er3+ doping. The higher efficiency for DSSC with the tri-layer electrode is mainly attributed to the down-conversion luminescence effect by Eu3+ ions from ultraviolet light to visible light and up-conversion luminescence effect by Er3+ ions from infrared light to visible light.