Display omitted •Non-flammable electrolyte with TMP and F-EPE improves the safety of SIB.•TMP/F-EPE electrolyte stabilizes the interface of NFM cathode during all processes.•The cycling life of NFM/HC pouch cell increases by using TMP/F-EPE electrolyte. Despite their beneficial effect on battery safety, non-flammable electrolytes often have an adverse side effect on the electrochemical performance of lithium and sodium ion batteries due to their poor compatibility with the electrodes. In this paper, we report a new non-flammable electrolyte consisting of trimethyl phosphate (TMP) and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (F-EPE) as non-flammable solvents and fluoroethylene carbonate (FEC) as additive with different concentration of Na salts, and a EC-DEC-FEC electrolyte was also prepared as baseline electrolyte. The flammability and non-flammability of the prepared electrolytes was tested. It is shown that the prepared electrolyte not only increases the capacity (129.9 vs. 122.5 mAh g−1 of baseline electrolyte) of NaNi1/3Fe1/3Mn1/3O2 (NFM) cathode but also stabilizes the cyclability (70.8% retention after 500 cycles) of NFM/HC (HC: hard carbon) pouch cells. The dissolution of pristine NaNi1/3Fe1/3Mn1/3O2 cathode material in different solvents and electrolytes, and the XPS patterns of the cycled NFM cathode in the prepared electrolytes were also studied to understand the capacity fading mechanism. These results indicate that this new non-flammable electrolyte holds great potential for application in rechargeable sodium-ion batteries.