Different weight percentage (2, 3, 4, and 5 wt %) of polyaniline (PANI) were incorporated into electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) composite membranes (esCPMs). The regular morphology, molecular structure, crystallinity, porosity, electrolyte uptake, and leakage of the composite membranes were examined. The esCPMs were activated in liquid electrolyte containing 0.5 M LiI, 0.05 M I-2, and 0.5 M 4-tert-butylpyridine and 0.5 M 1-butyl-3-methylimidazoliun iodide in acetonitrile to afford electrospun PVdF-HFP/PANI composite membrane electrolytes (esCPMEs). The influence of different wt % of PANI on the esCPMEs was studied by electrochemical impedance measurements and Tafel polarization studies. The photovoltaic performance of a dye-sensitized solar cell assembled using 3 wt % PANI incorporated esCPME exhibits a higher power conversion efficiency of 7.20% than that assembled using esPME (=6.42%).