Electrolyte plays a vital role in determining battery performances, while the effect of solvent molecular interaction on electrode performances is not fully understood yet. Herein, we present an unrevealed dipole–dipole interaction to show the mechanism of solvent interaction effect on stabilizing the electrolyte for high electrode performances. As a paradigm, a new nonflammable triethyl phosphate (TEP)-based electrolyte is designed to stabilize the bulk alloying anode (e.g., Sb), where an interfacial model is constructed according to the solvation structure induced by the dipole–dipole interaction between TEP and the essential 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (HFE). We demonstrate that the Li+–solvent–anion complexes derived from different solvation structures exhibit different kinetic and electrochemical properties, contributing to varied Sb anode performances in different electrolytes. As a result, a high lithium storage capacity of 656 mAh g–1, robust rate capacities over 4 A g–1, and a long lifespan of more than 100 cycles are achieved, which are better than those reported before. This work presents a different insight into understanding electrolyte effects on electrode performances and provides a guideline for electrolyte design to stabilize alloying anodes and beyond in metal-ion batteries.