Nickel-rich lithium nickel cobalt manganese oxides have received considerable attention as a promising cathode material, however, they have suffered from poor interfacial stability, especially at high temperature. Here, we suggest a bi-functionalized divinyl sulfone that enhances the applicability of a nickel-rich cathode via stabilization of the electrolyte–electrode interface. The divinyl sulfone forms a protective layer on the cathode surface by electrochemical oxidation reactions and this greatly decreases the internal pressure of the cell via stabilization of the Ni-rich cathode–electrolyte interface. The cell controlled with divinyl sulfone shows remarkable cycling performance with 91.9% capacity retention at elevated temperature even after 100 cycles. Additional electrode analyses and first-principles calculations provide critical spectroscopic evidences to demonstrate the combined effects of the sulfone and vinyl functional groups. Once the divinyl sulfone is electrochemically oxidized, the vinyl functional groups readily participate in further stabilizing sulfone-based solid electrolyte interphase intermediates and afford a durable protective layer on the nickel-rich electrode surface.