Combining the advantage of metal, metal sulfide, and carbon, mesoporous hollow core–shell Sb/ZnS@C hybrid heterostructures composed of Sb/ZnS inner core and carbon outer shell are rationally designed based on a robust template of ZnS nanosphere, as anodes for high‐performance sodium‐ion batteries (SIBs). A partial cation exchange reaction based on the solubility difference between Sb2S3 and ZnS can transform mesoporous ZnS to Sb2S3/ZnS heterostructure. To get a stable structure, a thin contiguous resorcinol‐formaldehyde (RF) layer is introduced on the surface of Sb2S3/ZnS heterostructure. The effectively protective carbon layer from RF can be designed as the reducing agent to convert Sb2S3 to metallic Sb to obtain core–shell Sb/ZnS@C hybrid heterostructures. Simultaneously, the carbon outer shell is beneficial to the charge transfer kinetics, and can maintain the structure stability during the repeated sodiation/desodiation process. Owing to its unique stable architecture and synergistic effects between the components, the core–shell porous Sb/ZnS@C hybrid heterostructure SIB anode shows a high reversible capacity, good rate capability, and excellent cycling stability by turning the optimized voltage range. This novel strategy to prepare carbon‐layer‐protected metal/metal sulfide core–shell heterostructure can be further extended to design other novel nanostructured systems for high‐performance energy storage devices.