Anhydrous copper(II) fluoride (CuF2) has a high specific capacity of 528 mA h g−1with an operating voltage of 3.55 V vs. Li/Li+, achieving a high gravimetric energy density of 1874 W h kg−1, which makes it a promising cathode candidate for next-generation rechargeable lithium (Li) batteries. However, the notorious dissolution of Cu during charging triggers the rapid failure of the CuF2cathode, impeding its development. In this work, the reversibility of the anhydrous CuF2electrode was enabled viathe use of a fluorinated high-concentration (FHC) electrolyte to effectively suppress the dissolution of Cu. With the FHC electrolyte, the CuF2-Ketjen Black nanocomposite cathode delivered a reversible capacity of 228 mA h g−1after 30 cycles, which nearly tripled that of the baseline electrolyte. Thus, the strategy of electrolyte engineering is proposed to harness CuF2as a high-capacity cathode material for Li batteries.