As a power source, the power lithium-ion battery requires high capacity density, high rate capacity, good thermal stability as well as excellent cyclic stability. Electrospinning technique (EST), as a novel solution of preparing nanofibers, has been applied in lithium-ion batteries, such as separators with high surface area and porosity, to greatly enhance the electrochemical performance of power lithium-ion batteries. EST is mainly used for the preparation of high porosity nanofiber membrane, polymer blending membrane and inorganic-polymer composite membrane in order to improve the mechanical properties and thermal stabilities of separators. In addition, the obtained nanofiber materials using EST at cathodes or anodes can enhance the electrochemical performance. At last, the existing problems and the corresponding improvements of the regarding studies are pointed out.