In order to improve the electrochemical performance of lithium-ion batteries, a new kind of composite membrane made using inorganic nanofibers has been developed via electrospinning and the solvent-nonsolvent exchange process. The resultant membranes present free-standing and flexible properties and have a continuous network structure of inorganic nanofibers within polymer coatings. Results show that polymer-coated inorganic nanofiber membranes have better wettability and thermal stability than those of a commercial membrane separator. The presence of inorganic nanofibers in the polymer matrix enhances the electrochemical properties of battery separators. This results in lower interfacial resistance and higher ionic conductivity, leading to the good discharge capacity and cycling performance of battery cells assembled using polymer-coated inorganic nanofiber membranes. This provides a promising solution via which to improve conventional battery separators for the high performance of lithium-ion batteries.