An array of single-walled carbon nanotubes (SWCNTs) coated with photoelectro-polymerized bisphenol A (PBPA) films is first fabricated using visible light-assisted multiple voltammetry. The PBPA layers endow the highly ordered SWCNTs@PBPA with unique photoelectrochemical and photoelectrocatalytic properties. A pair of well-defined redox peaks appears at the formal potential of - 0.165 V (vs. SCE) for the SWCNTs@PBPA-based electrode, which shows a linearly increasing photocurrent response with increasing BPA concentration. Furthermore, the presence of PBPA on SWCNTs leads to a negative shift of 0.158 V for the oxidative peak potential of 0.05 mM ascorbate under light irradiation, and a positive shift of 0.468 V or 0.412 V for the reduction peak potential of 02 or H2O2, respectively. The SWCNTs@PBPA arrays show good catalytic activities towards the oxidation of ascorbate and the reduction of O-2. While simultaneously employing SWCNTs@PBPA as photoanode and cathode catalysts, the assembled ascorbate/O-2 fuel cell exhibits remarkably enhanced performances. The proposed fuel cell indicates open-circuit photovoltage of 0.693 V, short-circuit photocurrent density of 0.29 mA cm(-2) and maximum power density of 14.05 pW cm(-2) upon light illumination of 0.18 mW cm(-2) visible light.