Over the past two decades, the solid–electrolyte interphase (SEI) layer that forms on an electrode’s surface has been believed to be pivotal for stabilizing the electrode’s performance in lithium-ion batteries (LIBs). However, more and more researchers currently are realizing that the metal-ion solvation structure (e.g., Li+) in electrolytes and the derived interfacial model (i.e., the desolvation process) can affect the electrode’s performance significantly. Thus, herein we summarize recent research focused on how to discover the importance of an electrolyte’s solvation structure, develop a quantitative model to describe the solvation structure, construct an interfacial model to understand the electrode’s performance, and apply these theories to the design of electrolytes. We provide a timely review on the scientific relationship between the molecular interactions of metal ions, anions, and solvents in the interfacial model and the electrode’s performance, of which the viewpoint differs from the SEI interpretations before. These discoveries may herald a new, post-SEI era due to their significance for guiding the design of LIBs and their performance improvement, as well as developing other metal-ion batteries and beyond.

Sodium ion batteries (SIBs) are considered the most promising battery technology in the post‐lithium era due to the abundant sodium reserves. In the past two decades, exploring new electrolytes for SIBs has generally relied on the “solid electrolyte interphase (SEI)” theory to optimize the electrolyte components. However, many observed phenomena cannot be fully explained by the SEI theory. Therefore, electrolyte solvation structure and electrode–electrolyte interface behavior have recently received tremendous research interest to explain the improved performance. Considering there is currently no review paper focusing on the solvation structure of electrolytes in SIBs, a systematic survey on SIBs is provided, in which the specific solvation structure design guidelines and their consequent impact on the electrochemical performance are elucidated. The key driving force of solvation structure formation, and the recent advances in adjusting SIB solvation structures are discussed in detail. It is believed that this review can provide new insights into the electrolyte optimization strategies of high‐performance SIBs and even other emerging battery systems.