Photoelectrocatalytic (PEC) oxidation is an advanced technology that combines photocatalytic oxidation (PC) and electrolytic oxidation (EC). PEC activity can be greatly enhanced by the PC and EC synergy effect. In this work, novel copolymerized g-C3N4 (denoted as CNx)/TiO2 core-shell nanowire arrays were prepared by chemical vapor deposition. CNx were deposited on the surface of TiO2 nanowire arrays using organic monomer 4,5-dicyanidazole and dicyandiamide as copolymerization precursor. TiO2 nanowire arrays provide a direct and fast electron transfer path, while CNx is a visible light responsive material. After CNx deposition, the light response range of TiO2 is broadened to 600 nm. The deposition of CNx shell effectively improves the PC efficiency and PEC efficiency of TiO2. Under visible light irradiation and 1 V bias potential, the rate constant k of PEC degradation of CNx/TiO2 core-shell nanowire arrays is 0.0069 min−1, which is 72% higher than that of pure TiO2 nanowires. The built-in electric field formed in the interface between TiO2 core and CNx shell would effectively promote photogenerated charge separation and PEC activity.