Photocatalytic fuel cell (PFC) utilized the chemical energy contained in the molecules by combining photocatalytic treatment of wastewater with fuel cell electrochemical reaction. Herein, a PFC system with a novel dual S-scheme heterojunction CuBi2O4/Bi2WO6/ZnO nanorod array (CBO/BWO/ZnO NRA) composite photoanode was first constructed for municipal wastewater treatment accompanied with electricity generation under direct sunlight. The introduction of CBO and BWO not only contributed to the narrowing of the band gap which enabled the ZnO NRA to utilize sunlight more efficiently, but also led to the excellent electron-hole segregating capability. The 10 CBO/BWO/ZnO NRA composite photoanode achieved a significantly ameliorated electrical power with maximum power density of 7.707 µW/cm2, which was superior to those pristine ZnO NRA and BWO/ZnO NRA binary materials. The composite photoanode was then tested for its mineralization activity in the municipal wastewater and 98.4 of COD removal was acquired within 90 min. The main attribution that conducive to its spectacular performance in municipal wastewater treatment came from the one-dimensional nanorod array architecture along with the synergistic relation among the three efficient components in the CBO/BWO/ZnO NRA heterojunction that can effectively hinder the charge carrier recombination rate and facilitated a good route for electron transport. The composite photoanode also manifested good stability in five cyclic runs. The dual S-scheme CBO/BWO/ZnO NRA enabled the free active species partook in the photoelectrocatalytic reaction and the working principle of PFC system was also speculated. Additionally, phytotoxicity findings signified that the comprehensive toxicity of municipal wastewater was eliminated after PFC treatment. © 2023 Elsevier Ltd