A new bifunctionalized TiO(2) film containing a dye-sensitized region and a degradation region was described. A similar structure of dye-sensitized solar cell (DSSC) was fabricated in the dye-sensitized region to accomplish separation of electrons from positive charges, and separation of dye from pollutants to avoid dye decomposition. The bifunctionalized TiO(2) film electrode and anode electrode can degrade methyl orange (MO) in reactors A and B, respectively. The degradation efficiency was enhanced remarkably by an external electrical potential. The decolorization of MO reaches as high as 95% after 2 h visible light irradiation at an external potential of 0.5 V along with a loss of 41% total organic carbon (TOC). The possible reason for the improvement of degradation by external DC potential was discussed. Effects of pH and inorganic salts on the decolorization are present.