The remarkable characteristics of nanofibers mats electrospun are large surface area to volume ratio and high porosity, which are crucial to increase the ionic conductivity of membrane full of liquid electrolyte, in this aspect, electrospinning is prior to the other methods, such as dry method, wet method, etc. Therefore, fabricating the separator of Li-ion batteries by electrospinning is potential and promising. The PVDF membranes were fabricated by electrospinning. The experiment demonstrated that the main deficiency in the fabricating separators process by electrospinning was low mechanical property, which induced partial short circuits inside the cells. Several methods were presented to enhance the mechanical strength. The experiments demonstrated that the higher the solution concentration was, the stronger the mechanical strength was, and the higher the voltage was, the stronger the mechanical strength was. Additionally, the spherical hat collection target instead of conditional plane target was applied in the electrospinning system, as a result, the thickness of the membrane was more uniform and the fiber diameter was also more uniform. Therefore, the charge and discharge capacity of the coin type cell composed of the separator collected by spherical hat target exceeded the plane target, and the electrospinning separators exceeded the commercial polypropylene separator.