This paper discusses the preparation of microporous fibrous membranes from PVdF solutions with different polymer contents, using the electrospinning technique. Electrospun PVdF-based fibrous membranes with average fiber diameters (AFD's) of 0.45–1.38μm have an apparent porosity and a mean pore size (MPS) of 80–89% and 1.1–4.3μm, respectively. They exhibited a high uptake of the electrolyte solution (320–350%) and a high ionic conductivity of above 1 × 10−3 s/cm at room temperature. Their ionic conductivity increased with the decrease in the AFD of the fibrous membrane due to its high electrolyte uptake. The interaction between the electrolyte molecules and the PVdF with a high crystalline content may have had a minor effect on the lithium ion transfer in the fibrous polymer electrolyte, unlike in a nanoporous gel polymer electrolyte. The fibrous polymer electrolyte that contained a 1M LiPF6-EC/DMC/DEC (1/1/1 by weight) solution showed a high electrochemical stability of above 5.0V, which increased with the decrease in the AFD The interfacial resistance (R i) between the polymer electrolyte and the lithium electrode slightly increased with the storage time, compared with the higher increase in the interfacial resistance of other gel polymer electrolytes. The prototype cell (MCMB/PVdF-based fibrous electrolyte/LiCoO2) showed a very stable charge–discharge behavior with a slight capacity loss under constant current and voltage conditions at the C/2-rate of 20 and 60°C.