To meet the demands of high-voltage lithium-ion batteries (LIBs), we develop a novel electrolyte through theoretical calculations and electrochemical characterization. Triphenylphosphine oxide (TPPO) is introduced as a film-forming additive into a sulfone-based electrolyte containing 1 mol L⁻¹ lithium difluoro(oxalate)borate. Density functional theory calculations show that TPPO has a lower reduction potential than the sulfone-based solvent. Hence, TPPO should be oxidized before the sulfone-based solvent and form a cathode electrolyte interphase layer on the Li-rich cathode. Our research findings demonstrate that adding 2 wt% TPPO to the sulfone-based electrolyte considerably enhances the ionic conductivity within a range of 20–60 ℃. In addition, it increases the discharge capacity of LIBs in a range of 2–4.8 V while maintaining excellent rate performance and cycling stability. Flammability tests and thermal gravimetric analysis results indicate excellent nonflammability and thermal stability of the electrolyte.