<p>Sodium metal batteries (SMBs) offer compelling advantages in resource abundance and cost, yet their practical deployment is hindered by the lack of electrolytes that simultaneously enable high-voltage stability, compatibility with the sodium metal anode, and rapid kinetics at low temperatures. Here, we develop a rationally engineered ether-ester hybrid electrolyte that addresses these long-standing trade-offs. By combining an ether solvent, diethylene glycol dimethyl ether, with a weakly solvating fluorinated ester, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate, the electrolyte spontaneously forms a unique solvation structure that promotes anion participation in the Na⁺ coordination sheath. This configuration lowers the Na⁺ desolvation energy barrier and directs the formation of robust interphases on both electrodes. As a result, the electrolyte exhibits high oxidative stability, excellent interfacial compatibility, and enhanced low-temperature kinetics. When paired with a high-voltage Na₃V₂(PO₄)₂O₂F cathode, the cell delivers exceptional cycling performance, retaining 97.8% of its initial capacity after 1000 cycles at a cut-off voltage of 4.3 V. Remarkably, it maintains 82.4% of its room-temperature capacity at −30 °C. This work establishes a new paradigm in electrolyte design, demonstrating that targeted solvation engineering can decouple key performance trade-offs and enable versatile SMBs under demanding conditions.</p>