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The aim of this study is to synthesis SPEEK composite proton exchange membrane with the addition of TiO2 nanofillers for microbial fuel cell application. SPEEK composite membrane with varying weight percentage of TiO2 (2.5, 5, 7.5 and 10%) was prepared to study the effect of TiO2 concentration on membrane performance. Synthesized composite membranes were subjected to various characterization studies such as FT-IR, XRD, Raman spectroscopy; TGA, UTM and SEM. Physico-chemical properties of membrane such as water uptake capacity, ion exchange capacity and thickness were also analyzed. 5% TiO2 – SPEEK composite membrane exhibited the higher water uptake capacity value and Ion exchange capacity value of 31% and 1.71 meq/g respectively. Performance of the MFC system with TiO2 – SPEEK membranes were evaluated and compared with the pristine SPEEK and Nafion membrane. 5% TiO2 – SPEEK membrane produced the higher power density (1.22 W/m2) and voltage (0.635 V) than the other membranes investigated. Efficacy of MFC in wastewater treatment was evaluated based on the chemical oxygen demand (COD), total organic carbon content and turbidity. Biofilm growth over the surface of the electrodes was also analyzed using scanning electron microscopy.