In recent years, microbial fuel cell (MFC) has been regarded as a promising technology for dye wastewater treatment. Compared with traditional anaerobic reactors, MFC has better decolorization effect while producing electricity simultaneously. In this paper, a double-chamber MFC with the sponge anode modified by polyaniline and chitosan-NCNTs was employed for simultaneous azo dye decolorization and bioelectricity generation. The influence of dye concentration, co-substrate concentration, and operating temperature on the performance of MFC with the modified anodes were studied. The results showed that a high decolorization efficiency (98.41%) and maximum power density (2816.67 mW m(-3)) of MFC equipped with modified bioanodes were achieved due to the biocompatibility and bioelectrocatalysis of modified material. And the biomass on the modified anode's surface was increased by 1.47 times. Additionally, microbial community analysis revealed that the modification of polyaniline and chitosan-NCNTs improved the selective enrichment of specific communities and the main microorganism was the electroactive and decolorizing bacteria Enterobacter (62.84%). Therefore, the composite anode is capable of fully utilizing the synergistic role of various materials, leading to superior performance of dye decolorization in MFCs. This work provided a strategy for the research on the recovery of biomass energy and decolorization in wastewater treatment.