The effect of applied anodic bias upon the photoelectrocatalytic degradation of methylene blue under ultraviolet illumination on nanoporous undoped TiO2/Ti electrode was studied in the present paper. The influence of doping different transition metal ions in TiO2/Ti on the degradation of methylene blue was also investigated.. The degradation degree was characterized with decolorization of methlylene blue. The results indicate that the degradation efficiency increases with increasing of the applied anodic bias up to 3.5 V, then decreases gradually. Doping TiO2 with Mn2+ and Cr3+ will enhance the efficiency of photoelectrocatalytic, while depositing Ni2+ on the TiO2 film shows a decrease of photoelectrocatalytic efficiency. The above metioned phenomena are attributed to ionic radii and the electron work functions values of the differently doped ions.