We demonstrate potential application of a new composite non-woven separator, which is comprised of a phase inversion-controlled, microporous polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP) gel polymer electrolyte and a polyethylene terephthalate (PET) non-woven support, to high-voltage and high-power lithium-ion batteries. In comparison to a commercialized polyethylene (PE) separator, the composite non-woven separator exhibits distinct improvements in microporous structure and liquid electrolyte wettability. Based on the understanding of the composite non-woven separator, cell performances of the separator at challenging charge/discharge conditions are investigated and discussed in terms of ion transport of the separator and AC impedance of the cell. The aforementioned advantageous features of the composite non-woven separator play a key role in providing facile ion transport and suppressing growth of cell impedance during cycling, which in turn contribute to superior cell performances at harsh charge/discharge conditions such as high voltages and high current densities.