A biobased ionic liquid crystal derived solid polymer electrolyte (BILC‐SPE) membrane, consisting of polymeric backbone, lithium salt, and cardanol derived ionic liquid crystals along with conventional plasticizer is fabricated using a facile and simple strategy. The in‐house prepared solid polymer electrolyte membrane within optimum concentration of individual counterparts has been deployed as electrolyte cum separator in lithium‐ion cells in combination with oxide and phosphate family cathodes individually to demonstrate its suitability and compatibility for energy storage applications. With carefully chosen 3‐(4‐(3‐pentadecylphenoxy) butyl)‐1‐methylimidazole‐3‐ium hexafluorophosphate as the ionic liquid crystal counterpart, the membrane exhibits high conductivity along with high porosity, wettability, and Li‐ion transport number owing to the presence of anisotropic channels that aid the facile transport kinetics desired for the cell performance. Promising results obtained regarding compatibility of cell components, excellent specific capacity, appreciable Coulombic efficiency, and cycling stability of the lithium‐ion cell investigated with BILC‐SPE developed from the low‐cost industrial waste not only revolutionize the performance of energy storage devices but also render a platform to create cleaner environment.