This work aims exploring the high performance porous separators that can be activated into gel electrolyte membranes for lithium ion batteries. A comb-like copolymer poly (dimethylsiloxane) graft poly (propylene oxide)-block-poly (ethylene oxide) (PDMS-g-(PPO-PEO)) was synthesized and blended with poly (vinylidene ﬂuoride) (PVDF) to fabricate porous separators via a typical phase inversion process, and then the separators absorbed liquid electrolyte solution and formed into polymer electrolyte membranes. By measuring the composition, morphology and ion conductivity etc, the influence of PDMS-g-(PPO-PEO) on structure and properties of blend separators were discussed. Compared with pure PVDF separator with comparable porous structure, the adoption of PDMS-g-(PPO-PEO) decreased the crystallinity and increased the liquid electrolyte uptake and stability effectively. It was also found that the electrode/electrolyte interfacial resistance could be reduced greatly. The resulting electrolyte membrane using separator with PVDF/PDMS-g-(PPO-PEO) mass ratio in 8/2 exhibited highest ionic conductivity in 4.5×10−3 S/cm at room temperature, while the electrochemical stability was up to 4.7V (vs. Li/Li+). Coin cells assembled with such separators also exhibited stable cycle performance and improved rate capabilities, especially when discharge rate higher than 0.5C.