• A novel electrolyte design strategy based on HOMO energy level and LCO absorption energy descriptors enables rational solvent selection for high-voltage LiCoO2 cathodes.
• The optimal solvent, tris(2,2,2-trifluoroethyl) phosphate, promotes a LiF-rich cathode/electrolyte interface that suppresses irreversible phase transitions and enhances Li+ diffusion kinetics.
• Graphite||HV-LCO pouch cells achieve 85.3% capacity retention after 700 cycles, wide-temperature operation (−60 to 80 °C), and pass nail penetration safety tests.
• This work provides a new paradigm for electrolyte engineering to construct stable interfaces for high-energy lithium-ion batteries, addressing both performance and safety challenges.