Electrospun Poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) nanofibrous composite membranes (esCPMs) incorporated with various wt% of polypyrrole (PPy) nanoparticles (1, 2, 3 and 4 wt%) were prepared by electrospinning technique for dye sensitized solar cell (DSSC) applications. The surface morphology, crystallinity, porosity and electrolyte uptake of the prepared esCPMs were examined. The esCPMs were soaked in an ionic liquid electrolyte containing 0.5M LiI, 0.05M I2, 0.5M 4-tert butyl pyridine and 0.5M 1-Butyl-3-methylimidazolium iodide in acetonitrile to get electrospun PVdF-HFP/PPy nanofibrous composite polymer membrane electrolytes (esCPMEs). The influence of PPy on ionic conductivity and electrocatalytic activity of esCPMEs were studied by electrochemical impedance and Tafel polarization measurements. The DSSC fabricated with esCPME (2wt% PPy) has the PCE of 7.02% at 100 mW cm-2, which is higher than that fabricated with the conventional electrospun PVdF-HFP membrane electrolyte (esPME).