High-energy-density lithium (Li) metal batteries are severely hindered by the dendritic Li deposition dictated by non-uniform solid electrolyte interphase (SEI). Despite its unique advantages in improving the uniformity of Li deposition, the current anion-derived SEI is unsatisfactory under practical conditions. Herein regulating the electrolyte structure of anions by anion receptors was proposed to construct stable anion-derived SEI. Tris(pentafluorophenyl)borane (TPFPB) anion acceptors with electron-deficient boron atoms interact with bis(fluorosulfonyl)imide anions (FSI - ) and decrease the reduction stability of FSI - . Furthermore, the type of aggregate cluster of FSI - in electrolyte changes, FSI - interacting with more Li ions in the presence of TPFPB. Therefore, the decomposition of FSI - to form Li 2 S are promoted, improving the stability of anion-derived SEI. In working Li | LiNi 0.5 Co 0.2 Mn 0.3 O 2 batteries under practical conditions, the anion-derived SEI with TPFPB undergoes 194 cycles compared with 98 cycles of routine anion-derived SEI. This work inspires a fresh ground to construct stable anion-derived SEI by manipulating the electrolyte structure of anions in working electrolytes.