Nano-TiO2 is selected as inorganic filler to fabricate the reduced crystalline composite polymer membrane. The porous polymer matrix employed in this study was poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) membrane synthesized via non-solvent evaporate method and the electrolyte solution uptake was carried out in the glove box to avoid the moisture contamination. The effect of nano-TiO2 on the crystalline of porous polymer membrane was studied. It was found that blending with nano-TiO2 helps to reduce the crystalline of polymer membrane. Electrochemical impedance spectroscopy showed that the room temperature conductivity of PVDF-HFP/TiO2 composite-porous polymer electrolyte (CPPE) increased up to 1.5 × 10−3S/cm, and scanning electron microscope (SEM) micrographs showed that the micro-pores and nano-TiO2 particles were observed in the polymer membrane. Furthermore, the composite-porous polymer electrolyte was stable up to 4.5 V (vs. Li/Li+) and the LiFePO4/CPPE/Li coin cell showed excellent rate capability, the discharge capacity obtained at 0.1C, 0.5C, 1C, and 3C were 164, 157, 143, and 122 mAh/g, respectively. And the cell had about 6 % capacity loss when it discharged at 1C for 50 cycles.