<p>In response to the growing demand for high-performance energy storage devices, this study focused on the development and characterization of novel electrolytes based on electrospun poly(vinylidene-co-hexafluoropropylene) (PVdF-HFP) fibrous membranes loaded with various concentrations of reduced graphene oxide (rGO). Lithium ions were incorporated into the novel electrospun PVdF/rGO fibrous membranes to form electrolytes, which were then sandwiched within a coin cell battery. The structural formation of the electrolytes was confirmed by Fourier transform infrared spectroscopy and Raman spectroscopy. The thermal properties were determined through thermogravimetric analysis and differential scanning calorimetry. The surface morphology of the samples was examined using scanning electron microscopy. The membranes exhibited high porosity and electrolyte uptake. The prepared cell delivered ionic conductivity in the order of 10⁻³&#xa0;S&#xa0;cm⁻¹, excellent cyclic stability with high discharge capacity and coulombic efficiency of 95%, and good lithium transference number. Overall, these findings highlight the potential of the developed PVdF-HFP/rGO electrolytes for high-performance energy storage applications.</p> Graphical Abstract <p></p>