The　plateau-type　sodium　titanate　with　suitable　sodiation　potential　is　a　promising　anode　candidate　for　high　safe　and　high　energy　density　of　sodium-ion　batteries　(SIBs).　However,　the　poor　initial　Coulombic　efficiency　(ICE)　and　cyclic　instability　of　sodium　titanate　are　attributed　to　the　unstable　interfacial　structure　along　with　the　decomposition　of　electrolytes,　resulting　in　the　continuous　formation　of　solid　electrolyte　interface　(SEI)　film.　To　address　this　issue,　a　chemical　grafting　method　is　developed　to　fabricate　a　highly　stable　interface　layer　of　inert　Al2O3　on　the　sodium　titanate　anode,　rendering　the　high　ICE　and　excellent　cycling　stability.　Based　on　theoretical　calculations,　NaPF6　are　more　likely　adsorption　on　the　Al2O3　surface　and　produce　sodium　fluoride.　The　formation　of　a　thin　and　dense　SEI　film　with　rich　sodium　fluoride　achieves　the　low　interfacial　resistances　and　charge-transfer　resistances.　Benefitting　from　our　design,　the　obtained　sodium　titanate　exhibits　a　high　ICE　from　67.7　%　to　79.4　%　and　an　enhanced　reversible　capacity　from　151　mAh　g−1　to　181　mAh　g−1　at　20　mA　g−1,　along　with　an　increase　in　capacity　retention　from　56.5　%　to　80.6　%　after　500　cycles.　This　work　heralds　a　promising　paradigm　for　rational　regulation　of　interfacial　stability　to　achieve　high-performance　anodes　for　SIBs.　©　2024　Wiley-VCH　GmbH.