The increasing of need for portable electrical energy makes the demand for rechargeable batteries high. Aluminum-ion battery with Solid Polymer Electrolyte (SPE) produced from the natural polymer corn starch with salt additive has the potential to be developed. The flexibility and resilience of SPE are enhanced by glycerol (C3H8O3). Throughing gelatinization of the linear monomer chains to become amorphous, the space for the ions in it is more free so that the ionic conductivity is high. By means of solution casting, heating temperature of 50°C for 9 hours found SPE with a strong structure. With the same concentration CS-Al has a higher conductivity with σ = 4.93 x 10-5 S/cm than CS-Na whose value is σ = 2,92 x 10-5 S/cm. This is due to the SPE CS-Al show more amorphous structure which allow more flexible ionic segmental motion. This is in accordance with XRD resulting which shows that the addition of aluminum nitrate salt is more amorphous than sodium acetate; the shift in peak pattern is also greater due to cation intercalation Al3+ with corn starch. FTIR is the result found that nitrate fixed by corn starch, indicated a change in the hydroxyl group of corn starch amylopectin. SEM photo of result also showed aluminum nitrate salt ion more easily in overcoming than sodium acetate. The indicate of SPE was more homogeneous because corn starch was already intercalated. They are combined to Al3+ and NO3- ions. With this value it can be an appropriate reference for developing SPE on Aluminum-ion batteries with aluminum nitrate salts have higher performance and environment friendly Keywords: Aluminum-ion battery, Solid Polymer Electrolyte, corn starch, ionic conductivity, and Amorphous