In the present work, an attempt has been made to develop nano aluminium oxide (Al₂O₃)-filled polyvinyl alcohol (PVA) composite gel electrolytes. Surface morphological studies, thermal behaviour, electrochemical stability and electrical characterization of these composite gel electrolytes have been performed. An increase in the concentration of Al₂O₃ in composite gel electrolytes increases the amorphous characteristics of pure PVA. Bulk conductivity of composite gel electrolytes increases by an order of magnitude on addition of a nano filler. Maximum conductivity of 5.81 × 10^-2 S/cm is observed for 6 wt% Al₂O₃-filled polymer gel composite electrolytes. Temperature dependence of electrical conductivity shows a combination of Arrhenius and Vogel–Tamman–Fulcher (VTF) nature. Maximum current stability during oxidation and reduction cycle is noticed for 6 wt% Al₂O₃-filled PVA composite electrolyte, viz. ±1.65 V.