Employing linear carbonates such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) as electrolyte solvents provides an opportunity to design appropriate electrolyte systems for high-performance sodium-ion batteries (SIBs). However, in practice, the use of linear carbonate-containing electrolytes is quite challenging because linear carbonates readily decompose at Na metal electrodes or sodiated anodes. One of the promising approaches is using an electrolyte additive to resolve the critical problems related to linear carbonates. Our investigation reveals that remarkable enhancement in electrochemical performance of Na4Fe3(PO4)2(P2O7) cathodes with linear carbonate-containing electrolytes is achieved by using a fluoroethylene carbonate (FEC) additive. Importantly, the initial Coulombic efficiency of the Na deposition/stripping on a stainless steel (SS) electrode is drastically improved from 16% to 90% by introducing the FEC additive into ethylene carbonate (EC)/propylene carbonate (PC)/DEC (5/3/2, v/v/v)/0.5 M NaClO4. The underlying mechanism of FEC at the electrode-electrolyte interface is clearly demonstrated by 13C nuclear magnetic resonance (NMR). In addition, the Na4Fe3(PO4)2(P2O7) cathode in EC/PC/DEC (5/3/2, v/v/v)/0.5 M sodium perchlorate (NaClO4) with FEC delivers a discharge capacity of 90.5 mAh g−1 at a current rate of C/2 and exhibits excellent capacity retention of 97.5% with high Coulombic efficiency of 99.6% after 300 cycles at 30 °C.