High　initial　coulombic　efficiency　is　highly　desired　because　it　implies　effective　interface　construction　and　few　electrolyte　consumption,　indicating　enhanced　batteries＇　life　and　power　output.　In　this　work,　a　high-capacity　sodium　storage　material　with　FeS2　nanoclusters　(approximate　to　1-2　nm)　embedded　in　N,　S-doped　carbon　matrix　(FeS2/N,S-C)　was　synthesized,　the　surface　of　which　displays　defects-repaired　characteristic　and　detectable　dot-matrix　distributed　Fe-N-C/Fe-S-C　bonds.　After　the　initial　discharging　process,　the　uniform　ultra-thin　NaF-rich　(approximate　to　6.0　nm)　solid　electrolyte　interphase　was　obtained,　thereby　achieving　verifiable　ultra-high　initial　coulombic　efficiency　(approximate　to　92　%).　The　defects-repaired　surface　provides　perfect　platform,　and　the　catalysis　of　dot-matrix　distributed　Fe-N-C/Fe-S-C　bonds　to　the　rapid　decomposing　of　NaSO3CF3　and　diethylene　glycol　dimethyl　ether　successfully　accelerate　the　building　of　two-dimensional　ultra-thin　solid　electrolyte　interphase.　DFT　calculations　further　confirmed　the　catalysis　mechanism.　As　a　result,　the　constructed　FeS2/N,S-C　provides　high　reversible　capacity　(749.6　mAh　g(-1)　at　0.1　A　g(-1))　and　outstanding　cycle　stability　(92.7　%,　10　000　cycles,　10.0　A　g(-1)).　Especially,　at　-15　degrees　C,　it　also　obtains　a　reversible　capacity　of　211.7　mAh　g(-1)　at　10.0　A　g(-1).　Assembled　pouch-type　cell　performs　potential　application.　The　insight　in　this　work　provides　a　bright　way　to　interface　design　for　performance　improvement　in　batteries.