Abstract Solid electrolyte interphase (SEI) plays a crucial role in stabilizing the anode‐electrolyte interface of lithium‐ion batteries. To date, extensive efforts are dedicated to the regulation of the SEI's compositions, instead the dissolution of the SEI in the electrolyte, an important factor that significantly influences the interfacial stability, received less attention. In this work, it is discovered for the first time that the dissolution of propylene carbonate (PC)‐derived SEI can be restrained by employing tetramethylene sulfone (TMS) as the main solvent, thereby markedly enhancing the interfacial stability of Li||graphite half‐cell and high‐voltage graphite||LiCoO 2 full cell. Undoubtedly, this work provides a new electrolyte design principle for developing many solvents that are previously considered detrimental in batteries to establish robust interfaces by minimizing the solubility of SEI.