Currently, scientific developments in both the academic and industrial research communities are giving much attention towards the development of green chemistry secondary ion batteries with safety attributes. Biodegradable starch polymer-based electrolyte systems doped with different inorganic salts are gaining much attention owing to their intriguing and non-toxic nature. In this context, several research approaches have been identified for the improvement of lithium-ion conductivities at ambient temperatures, thermal and mechanical properties of starch polymer-based electrolytes. The present review provides consolidated information on chronological developments in the fabrication of different types of starch-based electrolytes (i.e., pure, blend, plasticized, and nanocomposites) and discusses microstructural, thermal, mechanical, and lithium-ion conductivity properties given lithium-ion batteries. Among all types, ionic liquids doped starch-based electrolytes demonstrated appreciable room temperature Li-ion conductivities. In parallel, a comparative study on Na + , K + , NH 4 + , Ag + , and Mg 2+ -ions conductivities in starch-based electrolytes is presented to emphasize the further research scope on the development of novel secondary ion batteries in complementing with lithium-ion batteries.