For sodium batteries, the development of gel polymer electrolytes (GPEs) with remarkable electrochemical properties is in its early stage and persists to be a challenge. In this report we have synthesized a series of GPEs containing a poly(vinyllidene fluoride-co-hexafluoropropylene) (PVdF-HFP) and poly (methyl methacrylate) (PMMA) as blend polymer, sodium perchlorate (NaClO4) as ion-conducting salt and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) and tetra ethylene glycol dimethyl ether (TEGDME) as molecular solvents. The counter balance between EMIM-BF4 and TEGDME is maintained by the electrolyte, which is formed through the optimal weight ratio of 2 : 1. GPEs have an advantageous set of properties, including stability window of 5 V, Na+ transference number of 0.20, and a room-temperature ionic conductivity of 5.8 × 10-3 S cm-1. According to enthalpy and entropy calculations, optimized GPE yields the highest amount of disorder or amorphicity and contributes to greatest conductivity. XRD analysis supports this argument. Thermal investigations show that optimized GPE may preserve gel phase up to 125 °C. The prototype sodium cell fabricated with optimize GPE has a specific capacity of 281 mA h g-1 and open circuit voltage of 2.5 V. The optimized GPE exhibits potential for future electrochemical applications.