The redox stabilities of different oxygen donor solvents (C═O, P═O and S═O) and lithium salt anions for supercapacitors (SCs) electrolytes have been compared by calculating the frontier molecular orbital energy. Among six lithium difluoro(oxalate)borate (LiDFOB)‐based mono‐solvent electrolytes, the dilute LiDFOB‐1,4‐butyrolactone (GBL) electrolyte exhibits the highest operating voltage but suffers from electrolyte breakdown at elevated temperatures. Trimethyl phosphate (TMP) exhibits the highest redox stability and a strongly negative electrostatic potential (ESP), making it suitable for promoting the dissolution of LiDFOB as expected. Therefore, TMP is selected as a co‐solvent into LiDFOB‐GBL electrolyte to regulate Li+ solvation structure and improve the operability of electrolytes at high temperatures. The electrochemical stable potential window (ESPW) of 0.5 m LiDFOB‐G/T(5/5) hybrid electrolyte can reach 5.230 V. The activated carbon (AC)‐based symmetric SC using 0.5 m LiDFOB‐G/T(5/5) hybrid electrolyte achieves a high energy density of 54.2 Wh kg−1 at 1.35 kW kg−1 and the capacitance retention reaches 89.2% after 10 000 cycles. The operating voltage of SC can be maintained above 2 V when the temperature rises to 60 °C.