Poly(vinylidene fluoride)-polyacrylonitrile-based membranes containing Fe2O3 nanoparticles were prepared by electrospinning technique and characterized by HR-SEM, FTIR, and XRD analysis. The effect of electrolyte in the electrospun nanofibers on electrolyte uptake, ionic conductivity and porosity were studied. The electrospun membranes containing Fe2O3 showed an enhanced ionic conductivity than that of without Fe2O3. Among the prepared membranes, the membrane with 7 wt % Fe2O3 has the highest liquid electrolyte uptake of 562% and ionic conductivity of 6.81 × 10−2 S cm−1. The photovoltaic performance for open circuit voltage (Voc), Short-circuit current density (Jsc), Fill factor (FF), and η of the DSSC fabricated with 7 wt % Fe2O3 are 0.77 V, 10.4 mA/cm2, 0.62 and 4.9%, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41107.