Tailoring Electrolyte Chemistry Through Precise Organic Synthesis for Lithium Metal Batteries

ABSTRACT Realizing next‐generation batteries with specific energies exceeding 500 Wh kg −1 requires coupling lithium metal anodes with high‐voltage cathodes. Conventional carbonate electrolytes fundamentally fail in these aggressive environments due to narrow electrochemical windows and catastrophic interfacial degradation. Overcoming these bottlenecks demands a paradigm shift from empirical formulation to rational molecular design. This review highlights synthetic molecular engineering as a systematic framework to tailor electrolyte chemistry at the atomic scale via precision organic synthesis—defined as deliberate covalent modification including de novo construction and targeted functionalization, focused herein on lithium metal systems. By employing precise organic synthesis through electronic regulation, steric hindrance modulation, and functional group integration, researchers actively program the physicochemical properties of salts, solvents, and additives. We systematically elucidate how these engineered components remodel primary solvation structures and direct the construction of robust interphases, navigating the long‐standing trade‐off between ionic conductivity and stability. We further benchmark performance against practical pouch‐cell constraints and distill conditional design rules specifying where each strategy succeeds and fails. Finally, integrating computational screening, perfluoroalkyl and polyfluoroalkyl substances (PFAS) sustainability considerations, and green synthesis will accelerate the industrial translation of advanced industrial lithium metal energy storage.