The current investigation presents comparative studies on the effect of introducing three different molecular liquid solvents, namely ethylene carbonate: diethyl carbonate (EC:DEC), tetra ethylene glycol dimethyl ether (TEGDME), and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) on the electrochemical and physical properties of sodium ion conducting polymer gel electrolytes (PGEs) containing sodium tetrafluoroborate (NaBF4) salt, and polyvinyllidene fluoride-co-hexafluoropropylene (PVdF-HFP) polymer. The PGE, which is optimized and contains the EC: DEC solvent, has an ionic conductivity of 8.9 × 10−4 S cm−1, electrochemical stability of 4.5 V and total ion transport number of 0.99 at 30 °C. Along with conductivity studies, the X-ray diffraction studies, show that the EC: DEC raises the entropy of the PGE to its maximum value. The thermogravimetric (TGA) and differential scanning calorimetry (DSC) investigations demonstrate that electrolyte with EC: DEC exhibits a weight loss of 13 % up to 200 °C and retain the gel phase up to 140 °C. The optimized electrolyte holds promise for forthcoming sodium based electrochemical devices.