This study presents the possibility of generating electricity from a single culture microbial fuel cell (MFC), using polyvinylidene fluoride (PVDF)/Nafion composite membranes. Electrospun PVDF nanofibres were fabricated using an electrospinning method. The membranes were prepared by combining different amounts of Nafion (0.2 g, 0.4 g, 0.6 g) with high porosity electrospun PVDF nanofibres. The characteristics of the PVDF nanofibres and the membrane, such as morphology, thermal stability, structure and the power generated by the different PEMs, were investigated. Ribbon shaped PVDF nanofibres were preserved in a membrane, as shown by the Scanning Electron Microscopic (SEM) cross sectional image. Results from Thermogravimetric Analysis (TGA), X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) analysis show an increase in the thermal stability of the membrane due to the presence of the electrospun PVDF nanofibres. Consequently, the structure of the nanofibres was saved within the membrane. The results show that the membrane prepared using PVDF and 0.4 g Nafion had the highest power generation and coulombic efficiency of all membranes, with 4.9 mW/m2 and 12.1%, respectively. Meanwhile, the membrane prepared using PVDF and 0.2 g Nafion had the lowest power generation of 2.9 mW/m2 and a coulombic efficiency of 4.4%. (C) 2014 Elsevier B.V. All rights reserved.