The coated separator was prepared by coating poly(vinyl acetate) (PVAc) on the surface of the novel separator based on poly(vinylidene fluoride) (PVdF) and polyethylene (PE) non-woven matrix. The ionic conductivity of the coated separator was 1.1 × 10−3 S cm−1 at 25 °C, a little higher than that of bare separator. The coated separator showed smoother surface morphology and better adhesion property toward electrodes, and thereby it resulted in lower total resistance than the bare separator. The discharge capacity of the unit cell with coated separator at C/2 rate was maintained at about 84% of the theoretical capacity, which is quite higher than that of the unit cell with the bare separator.