<p>Heterostructures, consisting of metal selenides and metal sulfides, have been extensively reported as hosts for sulfur (S), aiming to address three significant challenges confronted by S cathodes in lithium-sulfur batteries. To answer the key question—whether a heterostructure of metal selenides or metal sulfides is a better choice as the host for an S cathode —two types of zeolitic imidazolate framework (ZIF)-8-derived ZnSe@VSe₂ and ZnS@VS₂ polyhedra are designed and successfully synthesized. Results show that ZnSe@VSe₂/NC (nitrogen-doped carbon) host possesses stronger anchoring and catalytic conversion abilities (Li₂S precipitation capacity: 178.97 mAh·g⁻¹) to polysulfides than ZnS@VS₂/NC host (107.79 mAh·g⁻¹). Meanwhile, ZnSe@VSe₂/NC@S cathode presents fast S redox and Li⁺ diffusion kinetics, superior charge-discharge stability, and low electrochemical polarization. As a result, ZnSe@VSe₂/NC@S cathode exhibits significantly better cycling performance (525 mAh·g⁻¹ at 1C after 300 cycles) and rate capability than ZnS@VS₂/NC@S cathode (378 mAh·g⁻¹). These advantages are primarily attributed to the synergistic effects arising from the built-in electric field at the ZnSe@VSe₂ heterointerface (directed from VSe₂ to ZnSe), the lower electronegativity of Se compared to S, and the higher electrical conductivity of ZnSe/VSe₂ relative to ZnS/VS₂.</p> Graphical Abstract <p></p>