Microbial fuel cells (MFCs) have been widely used in the treatment of organic wastewater because of its advantages of high efficiency, environmental friendliness, and no secondary pollution. In this study, we developed a composite anode, CeO2@Co3O4-PEDOT/CF (PEDOT: poly(3,4-ethylenedioxythiophene), CF: carbon felt), by incorporating bimesoporous CeO2@Co3O4 nanoparticles and PEDOT layer. The MFCs equipped with this novel anode had demonstrated exceptional catalytic performance in the treatment of Polyoxymethylene (POM) wastewater. Specifically, it achieved a 74.9 % increase in output voltage (586 ± 23 mV), a 2.5-fold increase in power density (3564 ± 27 mW/m2), and enhancements of 41.8 %, 40.1 %, and 47.0 % in the degradation rates of formaldehyde (HCHO, 97.2 %), 1,3,5-trioxane (TOX, 93.6 %), and chemical oxygen demand (COD) removal efficiency (84.4 %), respectively, when compared to a bare CF anode. Furthermore, the MFC with the composite anode demonstrated high degradation efficiency and COD removal efficiency across various industrial water environments. Additionally, the wheat seed germination experiments indicated a significant reduction in the toxicity of the degraded solution. This enhanced performance could be attributed to the synergistic effects of the bimesoporous CeO2@Co3O4 nanoparticles and the PEDOT layer. This study presents a promising strategy for the degradation of organic pollutants and the generation of bioelectricity in practical applications.