Anode with good electrocatalytic capabilities is more specifically required to reduce the ohimic losses during microbial fuel cell (MFC) operation. Highly conducive polymers viz., Polyaniline (PANi) and Polyaniline/Carbon nanotube (PANi/CNT) composite were prepared by in situ oxidative chemical polymerization method. Anodes were fabricated independently by coating PANi and CNT/PANi composites on the surface of SSM. The fabricated electrodes were evaluated as anode against stainless steel mess (SSM) as cathode during MFC operation. Maximum bioelectricity generation was observed in SSM-PANi/CNT-anode with power density of 48 mW/m(2) and COD removal efficiency of 80% compared with SSM-PANi-anode (38 mW/m(2); 65%) and SSM-anode (28 mW/m(2); 58%). Bioelectrochemical characterization of the electrode materials using cyclic voltammetry and electrochemical impedance spectroscopy showed high electrocatalytic activity of PANi/CNT composite electrode. The study concluded the efficiency of PANi/CNT composite electrodes as bioanode in operation of MFCs towards achieving increased bioelectricity production along with wastewater treatment.