Dye sensitized solar cell (DSSC) has been magnetizing more awareness in current research due to more efficiency. The foremost drawback of the solar cell is the evaporation of organic electrolyte. In order to address this problem, the polyvinylidene fluoride–polyacrylonitrile–Electrospinning Fibrous Membranes were prepared by electrospinning method and the photovoltaic performances were evaluated. The polyvinylidene fluoride and polyacrylonitrile were mixed in N,N′-dimethylformamide and acetone at an applied potential of 15 kV. The surface morphology of membrane is interconnected with network structure and a large number of voids were observed from Field Emission Scanning Electron Microscopy images. The electrolyte uptakes up to 310% were observed and it shows an increase in the ionic conductivity up to 6.12 × 10−2 S cm−1 at 25°C. The fabricated DSSCs show open circuit voltage (Voc) of 0.74 V, fill factor (FF) of 0.65 and short circuit current (Jsc) of 6.20 mA cm−2 at an incident light intensity of 100 mW cm−2. The photovoltaic efficiency also reached up to 3.09%. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40022.