Developing　advanced　anode　materials　for　sodium-ion　batteries　(SIBs)　is　a　frontier　and　hotspot　research　for　clean　and　sustainable　electricity　energy　storage　and　conversion.　However,　it　is　still　challenging　to　obtain　anode　materials　with　high　stability,　multiple　active　sites,　and　high　conductivity.　In　this　paper,　an　advanced　metal–organic　framework　(MOF)-based　anode　material　(Co-HITP),　which　integrates　multiple　advantages　into　one,　is　successfully　synthesized　through　a　sodiation-stimulated　in　situ　reconstruction.　The　Co-HITP　possesses　a　stable　single-crystal　structure,　expanded　spacing　layers,　abundant　sites,　and　good　conductivity,　and　exhibits　superior　properties　with　ultra-long　cycling　stability　(ultralow　decay　rate　≈0.001%　per　cycle　after　15 000　cycles　at　8 A g−1),　high　reversible　capacity　(450.1 mA h g−1　at　0.2 A g−1),　and　excellent　rate　performance.　Both　experimental　results　and　theoretical　calculation　reveal　that　the　anode　remains　a　stable　structure　after　long　cycling,　attributed　to　the　single-crystal　structure　with　d-π　hybridization　and　π–π　interaction,　and　the　minimum　structural　unit　stores　6Na+　ions　of　C═N　sites　and　8Na+　ions　of　aromatic　rings.　This　discovery　is　significant　for　developing　advanced　anode　materials　with　integrated　advantages　for　SIBs.　©　2024　Wiley-VCH　GmbH.