Gel polymer electrolytes (GPEs) were prepared with electrospun poly(vinylidene fluoride-co-hexafluoropropylene) [P(VdF-HFP)] nanofibrous membrane containing low molecular-weight polymer plasticizers, poly(ethylene glycol) dimethyl ether (PEGDME, Mw = 250 and 500). The fibers of electrospun membrane were stacked in layers to give fully interconnected pore structure with high porosity. The porous structure acted as a good host matrix to accommodate the polymer plasticizers. Thermogravimetric analysis (TGA) and field emission scanning electron microscope (FE-SEM) were used for thermal and physical characterizations, respectively. The GPEs exhibit high electrolyte uptake, high ionic conductivity, high anodic stability, and low interfacial resistance. Ionic conductivity and electrolyte uptake increased with the decrease in molecular weight of the polymer plasticizer. Prototype cells using electrospun P(VdF-HFP) nanofibrous GPEs with polymer plasticizers showed stable cyclic performances at different C-rates. (C) 2012 Elsevier B.V. All rights reserved.