Constructing　the　continuously-distributed　and　crystalline-NaF-rich　solid　electrolyte　interface　(CC-NaF-SEI)　is　expected　to　greatly　promote　the　sodium　storage　performance　of　hard　carbon　(HC)　anodes.　However,　such　an　impressive　concept　remains　extremely　intractable　to　achieve　and　lacks　an　efficiently　cost-less　strategy.　Herein,　the　application　of　the　commercially　available　LA133　binder　is　pioneered　to　engineer　such　a　CC-NaF-SEI.　Through　comparative　analysis　of　representative　binders　with　distinct　functional　groups,　reveals　the　critical　role　of　binder　chemistry　on　SEI　regulation.　Specifically,　the　LA133　binder　demonstrates　a　dual-regulation　mechanism　for　CC-NaF-SEI　formation.　The　anion-coordination　preferred　─CN　bonds　induce　an　anion-enriched　interfacial　solvation　structure,　and　the　─CONH/─CN　groups　catalytically　cleave　P─F　bond　dissociation　in　PF6−,　synergistically　promoting　anion　decomposition　kinetics　to　form　crystalline　NaF.　Furthermore,　robust　hydrogen　bonds　between　multiple　polar　groups　in　LA133　and　HC　surface　create　the　spatially　anion-confined　microenvironments　to　guide　orderly　anion　decomposition　and　facilitate　continuous　NaF　growth　into　a　mechanically　integrated　SEI.　The　optimized　CC-NaF-SEI　endows　HC　anodes　with　exceptional　sodium　storage　performance:　an　ultrahigh　initial　Coulombic　efficiency　(95.9%),　remarkable　reversible　capacity　(356.6　mAh　g−1),　and　stable　cycling　under　extreme　conditions　(−20–60 °C).　This　work　provides　fundamental　insights　into　binder-SEI　correlations,　establishing　a　novel　paradigm　for　interfacial　optimization　in　sodium-ion　batteries.　©　2025　Wiley-VCH　GmbH.