Evaporation-induced, close-packed silica (SiO2) nanoparticle-embedded polyethylene terephthalate (PET) nonwoven composite separator membranes (hereinafter, referred to as "NW-separators'') are fabricated for application in high-voltage/high-rate lithium-ion batteries. The heat-resistant PET nonwoven is employed as a physical support to suppress thermal shrinkage of the NW-separator. A distinctive characteristic of the NW-separator is the well-connected interstitial voids formed between compactly packed SiO2 nanoparticles adhered by polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP) binders. This allows for the evolution of highly percolated, electrolyte-philic microporous architecture in the NW-separator. In comparison to a commercialized polyethylene (PE) separator, the NW-separator featuring the aforementioned structural uniqueness exhibits substantial improvements in porosity, air permeability, and electrolyte wettability, which contribute to the facile ionic transport and retarded growth of cell impedance during cycling. As a result, superior cell performance is obtained in the NW-separator. Notably, this advantageous effect of the NW-separator on cell performance becomes more pronounced at challenging charge/discharge conditions of high voltages (herein, 4.4V) and high current densities. (c) 2012 Elsevier B.V. All rights reserved.