MOF-derived Co₃SnC_0.7/Co₃Sn₂@NC composites with heterostructure were successfully prepared in this work. Typically, with hollow CoSn(OH)₆ as the precursor, ZIF-67 was coated on its surface by controlling Co²⁺ concentration and solvent, and then carbonized to obtain target products. During the calcination process, the hollow precursor interacts with the MOF material formed in situ on its surface, which not only realizes the regulation of product composition, but also forms a heterogeneous interface and an efficient conductive network. Co₃SnC_0.7/Co₃Sn₂@NC composites showed excellent sodium storage properties with the first discharge/charge specific capacity of 767/421 mAh·g⁻¹ at a current density of 100 mA·g⁻¹ and reversible specific capacity of 300 mAh·g⁻¹ after 100 cycles. The heterogeneous interface in the electrode material could increase the active site of sodium storage and promote the diffusion rate of sodium ions. The N-doped MOF-derived carbon layer and the inactive metal Co in Co₃SnC_0.7/Co₃Sn₂@NC not only improve Na⁺/e⁻ conduction rates, but also disperse the active material to prevent agglomeration. Our work provides a new strategy for rationally designing the structure and composition of energy materials.