Multiporous TiO2/Ti film electrodes were prepared by different anodic oxidation processes at low voltage, in which the micro-structured TiO2 thick films were prepared in H2SO4-H2O2-H3PO4-HF solution for 2 h and the nano-structured TiO2 thin films were prepared in H3PO4-HF solution for 30 min with post-calcination. Both types of TiO2/Ti films were characterized by scanning electron microscopy and X-ray diffraction analysis. The photocatalytic (PC) and photoelectrocatalytic (PEC) reactivity of the TiO2/Ti electrodes were evaluated in terms of bisphenol A (BPA) degradation in aqueous solution. The experimental results demonstrated that the nano-structured TiO2/Ti thin-film electrodes had higher reactivity in the BPA degradation reaction. The PEC degradation of BPA was further studied using different cathodes, either a reticulated vitreous carbon (RVC) electrode or a platinum (Pt) electrode. The experimental results confirmed that the efficiency of BPA degradation could be significantly enhanced in the TiO2/Ti-RVC reaction system due to the generation of H2O2 on the RVC cathode. It is believed that such a H2O2-assisted TiO2 PEC oxidation process may have good potential for water and wastewater treatment.