Metal sulfides have shown great promise for sodium‐ion batteries due to their excellent redox reversibility and relatively high capacity. However, metal sulfides generally suffer from sluggish charge transport and serious volume change during the charge–discharge process. Herein, potato chip‐like nitrogen‐doped carbon‐coated ZnS/Sb2S3 heterojunction (ZnS/Sb2S3@NC) is precisely synthesized through a sulfurization reaction, and a subsequent metal cation exchange process between Zn2+ and Sb3+. The theoretical calculations and experimental studies reveal the boosted charge transfer in ZnS/Sb2S3@NC composites. Therefore, the ZnS/Sb2S3@NC electrode exhibits excellent cycling stability (a high reversible capacity of 511.4 mAh g‐1 after 450 cycles) and superior rate performance (400.4 mAh g‐1 at 10 A g‐1). In addition, ZnS/Sb2S3@NC is based on a conversion‐alloy reaction mechanism to store Na+, which is disclosed by the X‐ray diffraction and high resolution transmission electron microscopy analysis. This effective synthesis method can provide a reference for the design of other high‐performance electrode materials for sodium‐ion batteries.