Lithium metal batteries (LMBs) have gained increasing attention owing to high energy density for large-scale energy storage applications. However, serious side reactions between Li anodes and organic electrolytes lead to low Columbic efficiency and Li dendrites. Although progress has been achieved in constructing electrode structures, the interfacial instability of Li anodes is still challenging. Solvation chemistry significantly affects the electrolyte properties and interfacial reactions, but the reaction mechanisms and the roles of each component in electrolytes are still vague. This review spotlights the recent development of electrolyte regulation with concentration and composition adjustments, aiming to understanding the correlation between solvation structures and Li anode stability. Further perspectives on the solvation design are provided in light of anode interfacial stability in LMBs.