AbstractHigh‐voltage lithium‐ion batteries (LIBs) enabled by high‐voltage electrolytes can effectively boost energy density and power density, which are critical requirements to achieve long travel distances, fast‐charging, and reliable safety performance for electric vehicles. However, operating these batteries beyond the typical conditions of LIBs (4.3 V vs Li/Li⁺) leads to severe electrolyte decomposition, while interfacial side reactions remain elusive. These critical issues have become a bottleneck for developing electrolytes for applications in extreme conditions. Herein, an additive‐free electrolyte is presented that affords high stability at high voltage (4.5 V vs Li/Li⁺), lithium‐dendrite‐free features upon fast‐charging operations (e.g., 162 mAh g⁻¹ at 3 C), and superior long‐term battery performance at low temperature. More importantly, a new solvation structure‐related interfacial model is presented, incorporating molecular‐scale interactions between the lithium‐ion, anion, and solvents at the electrolyte–electrode interfaces to help interpret battery performance. This report is a pioneering study that explores the dynamic mutual‐interaction interfacial behaviors on the lithium layered oxide cathode and graphite anode simultaneously in the battery. This interfacial model enables new insights into electrode performances that differ from the known solid electrolyte interphase approach to be revealed, and sets new guidelines for the design of versatile electrolytes for metal‐ion batteries.