Zero-sodium-excess　solid-state　batteries　(ZSBs)　are　promising　to　overcome　the　disadvantage　of　low　energy　density　for　Na-ion　batteries,　but　the　interfacial　issues　between　the　solid-state　electrolytes　and　current　collectors　remain　bottlenecks　for　their　practical　applications.　Herein,　we　report　a　self-regulated　stratification　of　the　artificial　interphase　through　the　conversion　reaction　between　MgF2　modification　layer　and　Na　metal.　Ascribed　to　the　huge　adsorption　energy　difference　between　Al–Mg　and　Al–NaF,　the　sodiophilic　Mg　concentrated　at　the　bottom　side　and　served　as　the　nucleophilic　seed　for　Na,　while　sodiophobic　NaF　on　the　top　side　provided　high　thermodynamic　stability　for　Na　dendrite　and　side　reaction　suppressions.　Consequently,　the　as　constructed　ZSBs　with　Na3V2(PO4)3　cathode　exhibited　prominent　energy　density　of　254.4　​Wh　kg−1　(calculated　based　on　the　total　mass　of　electrode　and　electrolyte)　with　a　capacity　retention　of　82.7%　over　350　cycles.　This　work　paves　a　feasible　way　to　achieve　high　performance　and　stable　ZSBs.　©　2024　The　Authors