Hard carbon (HC) is the most commonly used anode material in sodium‐ion batteries. However, the solid‐electrolyte‐interface (SEI) layer formed in carbonate ester‐based electrolytes has an imperceptible dissolution tendency and a sluggish Na+ diffusion kinetics, resulting in unsatisfactory performance of the HC anode. Given that electrode/electrolyte interface property is highly dependent on the configuration of Helmholtz plane, we filtrate proper solvents by PFBE (PF6‐ anion binding energy) and CAE (carbon absorption energy) and disclose the function of chosen TFEP to reconstruct the Helmholtz plane and regulate the SEI film on HC anode. Benefiting from the preferential adsorption tendency on HC surface and strong anion‐dragging interaction of TFEP, a robust and thin anion‐derived F‐rich SEI film is established, which greatly enhances the mechanical stability and the Na+ ion diffusion kinetics of the electrode/electrolyte interface. The rationally designed TFEP‐based electrolyte endows Na||HC half‐cell and 2.8 Ah HC||Na4Fe3(PO4)2P2O7 pouch cell with excellent rate capability, long cycle life, high safety and low‐temperature adaptability. It is believed that this insightful recognition of tuning interface properties will pave a new avenue on the design of compatible electrolyte for low‐cost, long‐life, and high‐safe sodium‐ion batteries.