Although　the　high-capacity　Sb2S3-based　anode　materials　for　sodium-ion　batteries　can　combine　the　advantages　of　multi-step　conversion　of　Sb2S3　to　Sb　and　alloying　reaction　between　Sb　and　Na　for　improving　the　performance,　the　slow　reaction　kinetics,　low　electronic　conductivity,　and　poor　reversibility　of　the　sodium　storage　process　have　limited　their　practical　application.　To　effectively　improve　the　electrochemical　performance,　a　three-dimensional　Sb2S3/S@S-doped　carbon　composite　with　a　hollow　core–shell　structure　based　on　the　combination　of　template　method　and　coupling　reaction　is　successfully　synthesized.　By　combining　the　finite　element　simulation,　dynamic　analysis,　and　density　functional　theory　calculation,　the　respective　roles　of　S-composite　and　hollow　core–shell　structure　in　boosting　performance　are　revealed.　The　internal　S　and　external　S-doped　carbon　can　interact　with　Sb2S3　to　improve　its　reactivity　with　Na+,　and　effectively　release　the　stress　of　Sb2S3　in　the　sodiation　process.　The　S-doped　carbon　can　accelerate　Na+　diffusion　and　further　stabilize　the　structure　of　Sb2S3.　Benefited　from　the　special　structure,　the　as-prepared　anode　displays　high　reversible　capacity,　superior　cycle　performance　and　high　rate　capability.　The　assembled　full　battery　also　exhibits　an　excellent　energy　density　under　high　power,　and　can　still　maintain　a　high　reversible　capacity　of　310　mAh/g　at　1　A/g　over　500　cycles.　©　2022　Elsevier　B.V.