Reconfiguring the electrolyte microstructure containing Li+ solvation structure in bulk electrolyte and Helmholtz layer (HL) near the interface presents a compelling strategy in the design of electrolytes. In this work, ionic liquids (ILs) and partially solvated fluorobenzene (FB) build the unique Li+ coordination state modulated by FB and dominated by anions as well as a HL enriched in non-sacrificial cations on charging. As an important part to regulate the micro environment, FB not only enhances the ion transport kinetics of electrolyte and promotes the interaction of Li+-FSI−, but also participates in constructing a robust solid electrolyte interphase (SEI). Interestingly, FB indirectly promotes the enrichment of ILs’ cations at the HL, which is beneficial for uniform Li metal deposition due to its electrostatic shielding effect. Lithium metal batteries utilizing this electrolyte demonstrate impressive cycling performance at a high rate (approximately 89% capacity retention after 2,500 cycles at 5 C). Furthermore, these cells show excellent high-temperature performance, maintaining 71% of the initial capacity after 1,000 cycles at 70°C and 10 C rate.