Functional electrolyte is the key to stabilize the highly reductive lithium (Li) metal anode and the high-voltage cathode for long-life, high-energy-density rechargeable Li metal batteries (LMBs). However, fundamental mechanisms on the interactions between reactive electrodes and electrolytes are still not well understood. Recently localized high-concentration electrolytes (LHCEs) are emerging as a promising electrolyte design strategy for LMBs. Here, we use LHCEs as an ideal platform to investigate the fundamental correlation between the reactive characteristics of the inner solvation sheath on electrode surfaces due to their unique solvation structures. The effects of a series of LHCEs with model electrolyte solvents (carbonate, sulfone, phosphate, and ether) on the stability of high-voltage LMBs are systematically studied. The stabilities of electrodes in different LHCEs indicate the intrinsic synergistic effects between the salt and the solvent when they coexist on electrode surfaces. Experimental and theoretical analyses reveal an intriguing general rule that the strong interactions between the salt and the solvent in the inner solvation sheath promote their intermolecular proton/charge transfer reactions, which dictates the properties of the electrode/electrolyte inter-phases and thus the battery performances.