For an efficient energy storage system, effective material is to be used. In the present work, novel poly(vinylidene fluoride)/titanium oxide (PVdF/TiO2) composite membranes were developed using electrospinning technique, as separator for supercapacitors. Different weight percentages of TiO2 nanoparticle (0, 5, 10, 15, and 20 wt%) were mixed with 20 wt% of PVdF in a 50:50 wt% of tetrahydrofuran and dimethylacetamide solvent. Various physical and electrochemical properties including fiber diameter, thermal stability, crystallinity, porosity, and electrolytic uptake were studied to identify the best membrane with optimum TiO2 wt% exhibiting superior characteristics. SEM and TGA studies revealed that the developed PVdF/TiO2 composite membrane with 10 wt% showed improved properties with a lower average diameter of about 66 +/- 8 nm, enhanced thermal stability up to 513.15 degrees C and higher porosity of 89%, respectively compared to other membranes. The crystallinity, ionic conductivity, and specific capacitance of the nonwoven separator membranes were determined using X-ray diffraction technique, electrolytic uptake, and charge-discharge studies, respectively. The present study revealed that the addition of TiO2 nanoparticles improved the physical and thermochemical properties of the separator membrane substantially and PVdF/TiO2 composite membrane with 10 wt% displayed superior performance compared to other membranes.