A hybrid composite membrane is prepared by coating nano-sized Al2O3 powder (13 and 50 nm) and poly(vinylidene fluoride-co-hexafluoropropene) (P(VdF-co-HFP)) binder on both sides of polyethylene separator. The composite membrane shows better thermal stability and improved wettability for organic liquid electrolyte than polyethylene separator, due to the presence of heat-resistant Al2O3 particles with high-surface area in the coating layer. By using the composite membrane, the lithium-ion cells composed of carbon anode and LiNi1/3Co1/3Mn1/3O2 cathode are assembled and their cycling performances are evaluated. The cells assembled with the composite membranes are proven to have better capacity retention than the cell prepared with polyethylene separator, due to the enhanced ability to retain the electrolyte solution in the cell. The cell assembled with the composite membrane containing 13 nm-sized Al2O3 particles has an initial discharge capacity of 173.2 mA h g(-1) with good capacity retention.