Heterostructures are attracting increasing attention in the field of sodium‐ion batteries. However, it is still unclear whether any two monophase components can be used to construct a high‐performance heterostructure for sodium‐ion batteries, as well as the kind of heterostructures that can boost electrochemical performances. In this study, based on classical semiconductor theories on antiblocking and blocking interfaces, attempts are made to answer the abovementioned queries. For this purpose, NiTe2–ZnTe antiblocking and CoTe2–ZnTe blocking heterostructures are synthesized through a bimetal‐hexamine framework‐derived strategy. The NiTe2–ZnTe antiblocking heterostructure exhibits excellent high‐rate and cycling performances, while the CoTe2–ZnTe blocking heterostructure performs poorly, even compared to their monophase components. Further, kinetic measurements and theoretical calculation confirm that antiblocking heterointerfaces can boost Na‐ion diffusion efficiency and decrease the diffusion barrier, which can be attributed to the highly conductive antiblocking heterointerfaces generated due to electron transfer from NiTe2 to ZnTe. Therefore, this study provides a new perspective to design heterostructures more efficiently, with significantly better Na‐ion storage performance.