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An in-depth understanding of the electrode-electrolyte interaction and electrochemical reactions at the electrode-solution interfaces in rechargeable batteries is essential to develop novel electrolytes and electrode materials with high performance. In this perspective, we highlight the advantages of the interface-specific sum-frequency generation (SFG) spectroscopy on the studies of the electrode-solution interface for the Li-ion and Li-O2 batteries. The SFG studies in probing solvent adsorption structures and solid-electrolyte interpha