Mixtures of poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) and silica nanoparticles are coated on the surface of a silk fabrics separator. The coated separators are finally prepared by injecting an electrolyte solution and then characterized for use of lithium-ion battery separator/electrolyte. In the preparation, various contents of dibutylphthalate (DBP) as a plasticizer are used to enhance the formation of micropores within the coated membrane. The coated silk fabrics separators are characterized in terms of ionic conductivity, drenching rate, and electrochemical stability, and the charge-discharge profiles of lithium-ion batteries adopting the coated separators are also examined. As a result, the coated silk fabrics separator prepared using DBP 40~50 wt% and silica shows the superior separator properties and high-rate capability. This is due to (i) high sustainability of silk fabrics, (ii) the formation of micropores with the coated layer membrane by DBP, (iii) increase in drenching rate by silica nanoparticles to involve great enhancements in specific surface area and ionic conductivity.