Uniform TiO2/SiO2 composite films were prepared on ITO substrates by electrodeposition, and highly photoelectrocatalytic (PEC) activity of the composite films was observed toward the degradation of methyl orange (MO) in aqueous solutions. It was further found that their PEC activity was dependent on the electrodeposition parameters including deposition time, solution pH and SiO2 content. Under the optimized condition, the PEC degradation of MO on TiO2/SiO2 composite film electrode could be enhanced about 14 times relative to that on neat TiO2 film electrode. The high PEC activity of the TiO2/SiO2 composite film electrode was mainly attributed to the enhancement of the charge separation of photo-generated electron-hole pairs by the dispersion of SiO2 nanoparticles in the TiO2 matrix with the aid of the applied electric field.