In the present study, PVdF-co-HFP copolymer and its sulfonated derivatives have been analyzed as polymer electrolyte membrane in single chamber MFCs. The sulfonation of PVdF-co-HFP copolymer was performed by treating with chlorosulfonic acid for 5, 7 and 9 h, resulting in 23%, 30%, and 18% of degree of sulfonation (DS) in the respective SP-5, SP-7, and SP-9 membranes. On observing the membranes under field emission scanning electron microscope fitted with EDAX, porosity was found to be increasing with increase in the duration of sulfonation except for 9 h duration. The elemental analysis of the membranes indicated the presence of higher sulfur and oxygen content with the increasing sulfonation duration except for 9 h duration, for which crosslinks were formed via sulfone linkages. The membranes were characterized for their ion exchange capacity (IEC) and proton conductivity; IEC value of 0.21 meq g(-1) 0.42 meq g(-1), and 0.12 meq g(-1) and proton conductivity of 0.0012 S cm(-1), 0.00363 S cm(-1), and 0.0006 S cm(-1) were observed for SP-5, SP-7, and SP-9 membranes. Open air cathode MFCs with membrane electrode assemblies (MEA) containing sulfonated and non-sulfonated PVdF-co-HFP membranes have been analyzed for their overall MFC performance. It was observed that amongst these membranes, MFC with SP-7 membrane showed the maximum power and current density of 290.176 +/- 15 mW m(-2) and 1390.866 +/- 70 mA m(-2) with an overall similar to 89% COD removal in 28 days operation, using electrogenic mixed firmicute consortium. In overall, the study illustrates the impression of sulfonated PVdF-co-HFP membranes as PEM and its application in MFC for harvesting bio-energy. (C) 2014 Elsevier Ltd. All rights reserved.