A novel microbial fuel cell (MFC) anode is fabricated by electrochemically reducing graphene oxide (ERGNO) first and coating polyaniline (PANI) nano-fibers afterward on the surface of carbon cloth (CC). ERGNO/CC is prepared using an electrochemical synthesis method reducing graphene oxide by cyclic voltammetry (CV) in phosphate buffer solution (PBS, pH = 6.9). Combining the advantages of PANI and ERGNO, PANI–ERGNO/CC yields a maximum power density of 1390 mW m−2 when used as the MFC anode, which is 3 times larger than that of the MFC with the CC anode. The electrodes are characterized by scanning electron microscopy (SEM) and Raman spectroscopy. The electrochemical activities have been investigated by CV and electrochemical impedance spectroscopy (EIS). The great improvement is attributed to the fact that graphene not only serves as a highly conductive support material, but also provides large surface for PANI. High conductivity and large specific surface area greatly improve the charge transfer efficiency and the bacterial biofilm loading. In this work, a practical and promising synthesis method is developed to fabricate high-performance MFC anodes.