Carbonate electrolytes are commonly used in commercial non-aqueous Li-ion batteries. However, the high affinity between the solvents and the ions and high flammability of the carbonate electrolytes limits the battery operation temperature window to −20 to + 50 °C and the voltage window to 0.0 to 4.3 V. Here, we tame the affinity between solvents and Li ions by dissolving fluorinated electrolytes into highly fluorinated non-polar solvents. In addition to their non-flammable characteristic, our electrolytes enable high electrochemical stability in a wide voltage window of 0.0 to 5.6 V, and high ionic conductivities in a wide temperature range from −125 to + 70 °C. We show that between −95 and + 70 °C, the electrolytes enable LiNi0.8Co0.15Al0.05O2 cathodes to achieve high Coulombic efficiencies of >99.9%, and the aggressive Li anodes and the high-voltage (5.4 V) LiCoMnO4 to achieve Coulombic efficiencies of >99.4% and 99%, respectively. Even at −85 °C, the LiNi0.8Co0.15Al0.05O2 || Li battery can still deliver ~50% of its room-temperature capacity.