In this study, a novel polymer electrolyte composite membrane is successfully fabricated using electrospinning and solution casting. The composite membrane comprises two microporous poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) layers plus an intermediate quaternary ammonium-containing SiO2 nanoparticles modified polyethylene terephthalate (PET) nanofibrous nonwoven to form a sandwiched PVDF-HFP/PET/PVDF-HFP composite, which is employed as a separator for lithium-ion batteries (LIBs). The properties of the PET composite membrane are compared with those of commercial PE separator, such as the morphologies, physical properties, and electrochemical performances. According to our results, the composite membrane demonstrates superior thermal stability (thermal shrinkage similar to 8%), electrolyte-philicity (contact angle similar to 2.9(omicron)), electrolyte uptake and retention (282%, 74%), and ionic conductivity (similar to 10(-3) S cm(-1)). The separators are assembled into Li/LiFePO4 cells for electrochemical tests, showing that the PET composite membrane cells exhibit higher capacities than those with the PE separator at 0.2-10C both at 25 C-omicron and 55 C-omicron. The discharge capacity retention and coulombic efficiency of the PET composite membrane cells at 1C/1C for 200 cycles can be respectively enhanced about 20% and 2% at 55 C-omicron as compared to the PE separator cells. These results demonstrate that our prepared PET composite membrane is highly promising for LIB applications. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.