Hybrid Polyvinylidene fluoride/Octaphenyl-Polyhedral oligomeric silsesquioxane (PVDF/Octaphenyl-POSS) Lithium-ion battery separator (HPPS) was fabricated and characterized in this paper. HPPS membranes showed good compatibility of membrane matrix due to the organic-inorganic feature of OPS and OPS distributed in membranes very uniformly. Membranes with OPS also displayed commendable thermal stability, it showed nearly zero dimensional shrinkage after hot treatment. The mechanical property (12.7 MPa) of hybrid separators got strengthened after the addition of OPS nano particles which can satisfy the assembling and transportation of cells. Most reliable, separators showed an ionic conductivity of 4.2 x 10(-3) S/cm and the electrochemical window of 5.6 V. The first discharge capacity of battery with HPPS membrane reached 145.8 inAli/g and the discharge capacity retention was 81.5% from 0.1C to 2C. The HPPS separator was regarded as a promising candidate for the application in.Li-ion battery.