The optimized composition of PVdF-co-HFP–LiAlO2 based micro-porous nano-composite polymer electrolyte membranes (MPNCPEMs) was prepared with a preferential polymer dissolution process. Nitrogen adsorption isotherms and SEM micrographs showed that the enhanced ionic conductivity of polymer electrolyte was due to increase in pore-size, surface area and pore density, results an increase in the electrolyte uptake. The ac-impedance spectroscopy showed that the room temperature ionic conductivity of PVdF-co-HFP–LiAlO2 based polymer electrolyte membranes increased with the removal of PVA content and attained the maximum ionic conductivity of 8.12×10−3 Scm−1. The prepared MPNCPEM of high ionic conductivity was subjected into LSV study. Finally, the electrode/electrolyte interfacial resistance was evaluated by monitoring the impedance response at different time intervals.