The present work was to study silver electrodeposition on the activated carbon (AC) air cathode for performance improvement in microbial fuel cells (MFCs). The treated cathodes were proved to be effective to enhance the performance of MFCs. The maximum power density of MFC with silver electrodeposition time of 50 s (Ag-50) cathode was 1080 ± 60 mW m⁻², 69% higher than the bare AC air cathode. X-ray photoelectron spectroscopy (XPS) results showed that zero-valent, monovalent and divalent silver were present to transform mutually, which illustrated that the oxygen reduction reaction (ORR) at the cathode took place through four-electron pathway. From electrochemical impedance spectroscopy (EIS) analysis, the electrodeposition method made the total resistance of the electrodes largely reduced. Meanwhile the deposited silver had no toxic effects on anode culture but inhibited the biofilm growth of the cathodes. This kind of antimicrobial efficient cathode, prepared with a simple, fast and economical method, was of good benefit to the performance improvement of MFCs.