This study explores trivalent Al interaction with aqueous starch gel in the presence of two different anions through salting effect. Salting-out nature of Al2(SO4)3·18H2O with starch gel causes precipitation of starch; this happens due to competitive anion-water complex formation over starch-water interaction, thereby reducing polymer solubility. Salting-in effect of AlCl3 with starch gel happens through Al3+ cation interaction with hydroxyl group of starch and increases polymer solubility, making gel electrolyte viable for battery applications. Prepared gel electrolyte exhibits ionic conductivity of 1.59mS cm-1 and a high tAl 3+ value of 0.77. The gel electrolyte's performance is studied using two different cathodes, the Al|MoO3 cell employing starch gel electrolyte achieves discharge capacity of 193mA h g-1 and Al|MnO2 cell achieves discharge capacity of 140mA h g-1 @0.1 A g-1 for first cycle. The diffusion coefficient of both cells using starch gel electrolyte is calculated and found to be 2.1×10-11cm2 s-1 for Al|MoO3 and 3.1×10-11 cm2 s-1 for Al|MnO2 cells. The Al|MoO3 cell at lower temperature shows improved electrochemical performance with a specific capacity retention of ≈87.8% over 90 cycles. This kind of aqueous gel electrolyte operating at low temperature broadens the application for next generation sustainable batteries.