The formation of lithiophobic inorganic solid electrolyte interphase (SEI) on Li anode and cathode electrolyte interphase (CEI) on the cathode is beneficial for high-voltage Li metal batteries. However, in most liquid electrolytes, the decomposition of organic solvents inevitably forms organic components in the SEI and CEI. In addition, organic solvents often pose substantial safety risks due to their high volatility and flammability. Herein, an organic-solvent-free eutectic electrolyte based on low-melting alkali perfluorinated-sulfonimide salts is reported. The exclusive anion reduction on Li anode surface results in an inorganic, LiF-rich SEI with high capability to suppress Li dendrite, as evidenced by the high Li plating/stripping CE of 99.4% at 0.5 mA cm−2 and 1.0 mAh cm−2, and 200-cycle lifespan of full LiNi0.8Co0.15Al0.05O2 (2.0 mAh cm−2) || Li (20 µm) cells at 80 °C. The proposed eutectic electrolyte is promising for ultrasafe and high-energy Li metal batteries.