Conventional polyethylene (PE) separators are surface-modified by thin coating with conductive poly(3,4-ethylenedioxythiophen)-co-poly(ethylene glycol) (PEDOT-co-PEG) copolymer and aluminum fluoride particles. The surface-modified separators exhibit a significant reduction in thermal shrinkage and an improved electrolyte uptake. By using these separators, the lithium-ion cells composed of carbon negative electrodes and LiNi1/3Co1/3Mn1/3O2 positive electrodes are assembled and their cycling performances are evaluated. The cells assembled with the surface-modified separators demonstrate superior cycling performance compared to cells prepared with pristine PE separator, both at ambient temperatures and at elevated temperature.