Bioinspired materials have become increasingly competitive for electronic applications in recent years owing to the environment‐friendly alternatives they offer. The notion of biocompatible solid organic electrolytes addresses the issues concerning potential leakage of corrosive liquids, volatility and flammability of electrolyte solvents. This study presents a new intrinsically coordinated LiI adenine complex that exhibits electrical conductivity as a solid electrolyte capable of self‐sustained supply of LiI ions. It exhibits conductivity through moisture‐assisted LiI ion motion up to 373 K, and possibly by an ion‐hopping mechanism beyond 373 K. This purine‐derived solid electrolyte shows enhanced conductivity and transference number demonstrating the potential of purine‐based ligands and their coordination complexes in interesting materials applications.