Sodium metal is a promising anode for high-energy-density sodium rechargeable batteries (RSBs). However, the low Coulombic efficiency (CE) of the Na plating/stripping process and the problem of safety hinder their practical application. Herein, we report a facile strategy for employing the fluorinated phosphate solvents to realize highly reversible Na plating/stripping and improve the safety performance. The fluorinated phosphate molecules reduce the polarity of the solvent and lower the coordination number to Na+, which makes it possible to form the anion-induced ion–solvent-coordinated (AI-ISC) structures with high reduction tolerance. Moreover, the fluorination treatment enhances the oxidation resistance of the phosphate solvent, enabling compatibility with the high-voltage Na3V2(PO4)2F3 (NVPF) cathode. As expected, the Na@Al//NVPF full cell with the as-prepared 0.9 M NaFSI/tris­(2,2,2-trifluoroethyl) phosphate (TFEP) demonstrates a capacity retention of 83.4% after 200 cycles with an average CE of 99.6%. This work opens a new avenue for designing high-energy-density RSBs with improved safety performance.