The performance of microbial fuel cells (MFCs) consisting of exfoliated porous graphitic carbon nitride (ep-GCN) and its composite with acetylene black (AB) as cathode catalyst is evaluated. The cyclic voltammetry and electrochemical impedance spectroscopy of composite ep-GCN-AB indicated excellent oxygen reduction reaction activity and comparable charge transfer resistance with respect to Pt–C. The absence of X-ray diffraction peak at 2θ = 13° (corresponding to stacked structure of bulk GCN) indicated reduction in thickness. Four MFCs were operated with simulated wastewater with chemical oxygen demand (COD) of 3000 mg L−1. The maximum power densities of MFC-GAB (14.74 ± 0.17 W m−3), MFC-PAB (15.68 ± 0.58 W m−3) and MFC-G (12.47 ± 0.30 W m−3) using ep-GCN-AB, Pt–C and ep-GCN electrocatalyst, respectively, were 2.6, 2.7 and 2.2 times higher than MFC-AB operated with only acetylene black coated cathode. The investigation demonstrates that ep-GCN and its composites can be utilized as excellent cathode catalysts in MFCs at 20 folds lesser cost than Pt–C.