Superior sodium-ion-conducting polymer poly(vinyledene fluoride)–silicon dioxide (PVdF-SiO2) composite separator membrane was prepared via simple phase inversion method, which is a suitable alternative conventional polypropylene membrane. Basically, PVdF is the promising for use as high porous polymer electrolyte membrane due to its high dielectric constant (ε = 8.4). In this work, we prepared a composite membrane using PVdF-SiO2 via phase inversion method. This work was systematically studied towards the morphology, porosity, and electrochemical properties of as prepared membrane. The electrolyte uptake capability of separator membrane tested with 1 M NaPF6 electrolyte solution and temperature-dependent ionic conduction test were performed at various temperatures. This membrane exhibits higher ionic conductivity of 4.7 × 10−2 S cm−1 at room temperature. The physical properties were analyzed by X-ray diffraction, FT-IR, and FE-SEM micrographs analyses. The electrochemical performances with impedance analysis carried for prepared membrane with the as-prepared sodium P2-type cathode material. The material showed an initial discharge capacity of 178 mAh g−1 at 0.1 C between 2 and 4 V with 98% columbic efficiency and 81% capacity retention after 50 cycles upon using the as-prepared PVdF-SiO2 composite separator membrane.