The phosphorylated fullerene/sulfonated polyvinyl alcohol (PFSP) cation exchange membrane was prepared, characterized and its applications were studied in microbial fuel cell (MFC) for copper removal along with the power generation. The phosphorylation of fullerene was confirmed by UV and Fourier Transform Infrared Spectroscopy (FTIR). The composite membrane was prepared by solution casting method and characterized by FTIR, Scanning Electron Microscopy (SEM) and Thermo Gravimetric Analysis (TGA) methods. The proton conductivity, water uptake and ion exchange capacity (IEC) of the prepared membrane were observed to be 11.7 x 10(-2) S/cm, 120% and 1.67 meq/g respectively. Open circuit voltage (OCV) and power density obtained were 801 mV and 499.1 mW/m(2) respectively for the composite membrane. The maximum Cu++ removal was 73.2% as compared to 63.2% for Ultrex CMI 7000; a commercial membrane. This prepared membrane is expected to offer vital and constructive properties for its application in fuel cell technology and to remove copper ions from wastewater. (C) 2016 Elsevier B.V. All rights reserved.