A facile approach to the fabrication of nanoporous structure-tuned nonwoven composite separators is demonstrated for application in high-safety/high-rate lithium-ion batteries. This strategy is based on the construction of silica (SiO2) colloidal particle-assisted nanoporous structure in a poly(ethylene terephthalate) (PET) nonwoven substrate. The nanoparticle arrangement arising from evaporation-induced self-assembly of SiO2 colloidal particles allows the evolution of the unusual nanoporous structure, i.e. well-connected interstitial voids formed between close-packed SiO2 particles adhered by styrene-butadiene rubber (SBR) binders. Meanwhile, the PET nonwoven serves as a mechanical support that contributes to suppressing thermal shrinkage of the nonwoven composite separator. The aforementioned structural novelty of the nonwoven composite separator plays a key role in providing the separator with advantageous characteristics (specifically, good electrolyte wettability, high ionic conductivity, and benign compatibility with electrodes), which leads to the better cell performance than a commercialized polyethylene (PE) separator.