The preparation of 2,6-Bis(m-amino phenoxy) benzoyl naphthalene-based polyimides for solid polymer electrolytes was reported. Li-salt and PEO bearing polyimide membranes were prepared. Thermo-gravimetric analysis results reveal that the PI/PEO/LiCF 3 SO 3 polymer electrolyte membranes are thermally stable up to 500°C.The "T g " values are in the range 167-221.5°C according to dynamic mechanical analysis (DMA). The conductivities of Li-salt and PEO containing PI membranes are in the range of 10 −7 -10 −5 S/cm. The conductivity increases with incorporation of PEO and Li + concentration. The linear sweep voltammetry experiments showed that no peaks were observed between 1.75 and 4.5 V. K E Y W O R D Simpedance spectroscopy, Li batteries, polyimides, solid polymer electrolytes