Abstract: The conductivity, hydrophilicity, biocompatibility, and other characteristics of anode material in microbial fuel cell (MFC) can affect the adhesion, growth, metabolism and extracellular electron transfer of microorganisms, and its performance directly affects the important performance of MFC. Porous MXene/polypyrrole (MXene/PPy) hydrogels with three-dimensional structure were prepared by chemical oxidation, and the hydrogels were modified by phosphatization using sodium hypophosphite annealing. The electrochemical properties of the hydrogels before and after modification and the performance of the assembled MFC were studied using the hydrogel materials as anodes. The results showed that porous MXene/PPy hydrogels had good electrochemical properties. Phosphating exposed more reaction sites of MXene and further improved the electrochemical properties. When MXene/PPy hydrogel P-MXene/PPy-5 with specific phosphating degree (NaH₂PO₂ addition is 0.005 g/mL) was used as electrode material, the area specific capacitance and exchange current density increased to 948.55 F/m² and 0.73 mA/cm² respectively, while the charge transfer impedance decreased to 6.84 Ω. Compared with non-phosphating anode MFC, the maximum output power density of the assembled MFC increased by 49.62% to 7.87 W /m³, and the anode protein content increased by 37.53% to 59.07 mg/cm². This research result can provide an idea for developing higher-performance MFC in the future.