In this paper, firstly sulfonated polyethersulfone (SPES) was synthesized from polyethersulfone (PES) with sulfonation by chlorosulfonic acid as a sulfonating agent dissolved in concentrated sulfuric acid. PES/SPES blend proton exchange membranes (PEMs) were prepared at four different compositions with the non-solvent induced phase separation technique as alternative materials to Nafion membrane for application in a microbial fuel cell (MFC). The prepared PEMs were characterized by FTIR spectroscopy, AFM, SEM, contact angle, water uptake and oxygen permeability. Performances of the fabricated PEMs and commercial Nafion 117 were evaluated in a dual chamber MFC for treating of wastewater and electricity generation. Maximum generated power and current of the fabricated membranes were 58.726 mWm(-2) at current density of 317.111 mAm(-2), while it was 45.512 mWm(-2) at 228.673 mArn(-2) for Nafion 117 at the similar experimental condition. The observed properties of low biofouling, low oxygen permeability, high power generation, high COD removal and coulombic efficiency (CE) indicated that the SPES membrane has potential to improve significantly the productivity of MFCs. (C) 2017 Elsevier Ltd. All rights reserved.