The　continuous　rupturing　and　rebuilding　of　unstable　solid　electrolyte　interphase　(SEI)　layer　during　cycling　would　block　Na+　diffusion　and　induce　Na　dendrite　formation,　ultimately　limiting　the　practical　application　of　high-energy-density　sodium　metal　batteries.　Herein,　a　hybrid　SEI　layer　containing　Li-species　is　dexterously　constructed　on　the　surface　of　sodium　metal　anode.　Li-containing　inorganic　components　(Li3N,　LiF,　and　Li2CO3)　are　introduced　to　stabilize　the　Na/electrolyte　interface　and　enhance　the　mechanical　and　diffusion　kinetic　properties　of　the　SEI　layer,　which　can　reduce　the　side　reactions　and　gas　generation,　regulate　Na+　flux　during　cycling　and　promote　rapid　Na+　migration　for　uniform　dendrite-free　Na　deposition.　As　a　result,　the　constructed　Na　symmetric　cells　achieve　low　overpotential　and　long　cycle　life　of　5900,　1800,　and　500 h　at　current　densities　of　3,　10,　and　30 mA cm−2,　respectively.　Furthermore,　the　full　cells　paired　with　the　Na₃V₂(PO₄)₃　cathode　demonstrate　high　specific　capacity　and　excellent　cycle　stability,　even　at　an　ultra-high　cathode　loading　of　39.3 mg cm−2　and　a　low　N/P　ratio　(negative/positive　electrode　capacity　ratio　of　1.21).　©　2025　The　Author(s).　Angewandte　Chemie　International　Edition　published　by　Wiley-VCH　GmbH.