Microbial fuel cell (MFC) technology is getting acceptance as an emphatic, sustainable and energy efficient alternative of conventional wastewater treatment strategies. MFCs utilize exoelectrogens as biocatalysts to degrade the complex organic substances present in wastewater with simultaneous power generation. The present study was aimed at investigating the impact of MFC electrode’s modification with CeO2 nanoparticles and polyaniline (PANI) on its performance characteristics. The hydrothermal approach was employed for the synthesis of CeO2 nanoparticles followed by their deposition on carbon cloth (CC) as MFC cathode, whereas MFC’s anode i.e., CF/NF was modified by in-situe deposition of PANI. The synthesized material was characterized with FTIR, XRD, SEM, EDX and BET analysis. The experiments were performed using dual chambered MFC fed with leather tannery wastewater using modified and unmodified electrodes. The highest outcomes of power density and corresponding current density were observed with PANI@NF composite anode and CeO2@CC as cathode i.e., 279.3 mW/m2 corresponding to the current density of 581.8 mA/m2. The same MFC electrode configuration resulted in highest COD reduction, i.e., 80 % and coulombic efficiency of 19.86 %. On the other hand, MFC equipped with PANI@CF anode and CeO2@CC cathode also displayed comparable results. It was ascertained that modification of NF/CF anode with PANI (conductive polymer) and CC cathode with CeO2 nanoparticles have significantly improved the overall MFC operational performance regarding tannery wastewater treatment and bioelectricity generation.