Electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) membrane was prepared from a solution of 16 wt % of PVdF-HFP containing acetone/N,N-dimethyl acetamide (7:3 wt %). The prepared electrospun PVdF-HFP membrane (esPM) was then soaked in ionic liquid electrolyte containing 0.5M LiI, 0.05M I-2, and 0.5M 4-tert butylpyridine, 0.5M 1-butyl-3-methylimidazolium iodide (BMImI) in acetonitrile to get electrospun PVdF-HFP membrane electrolyte (esPME). The effect of various concentrations of BMImI containing esPME on ionic conductivity was studied by AC-impedance measurements and the I-/I-3(-) diffusion co-efficients was determined by linear sweep voltammetry. The photovoltaic performance of a DSSC fabricated using 0.5M BMImI containing electrospun PVdF-HFP membrane electrolyte (0.5M BMImI-esPME) has power conversion efficiency (PCE) of 6.42%. But the stability of the DSSC fabricated using 0.5M BMImI-esPME was considerably superior to that fabricated using 0.5M BMImI containing liquid electrolyte (0.5M BMImI-LE). (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42032.