The electrochemical deposition by a drastic potentiostatic procedure (by applying −2.2 V for 20 min) in cerium (IV) acid solution was used to deposit cerium-containing species on titan surface prepared by an anodic oxidation method at 120 V. Their morphologies and structures have been investigated by scanning electron microscopy and X-ray diffraction. The photoelectrochemical characteristics of the electrodes were investigated in methanol and 0.1 M NaOH. The result shows that doping titania with an appropriate amount of Ce can effectively improve its photocatalytic activity, and the optimum doping concentration is found to be relating to the first deposition (0.6 at.% of cerium (IV)) in our experiments.