Disulfide bonds have been recognized as key reversible linkages within the realm of dynamic covalent chemistry. Typically, the cleavage of S–S bonds has been accomplished through thiol- or metal sulfide-mediated disulfide exchange reactions. In this study, we report a novel Se–S dynamic exchange reaction as a highly efficient method for cleaving S–S bonds. Moreover, this groundbreaking research also explores and validates the mechanism of the dynamic reaction between Na 2Se and disulfides. This strategy has been successfully applied in organic synthesis to prepare benzothiazole derivatives from disulfides and either carbon disulfide or aromatic aldehydes, demonstrating highly efficient S–S bond cleavage, lowered dosage of S–S bond cleaving reagent, good tolerance toward various substituents and excellent yields. Consequently, the concept of a metal selenide-disulfide dynamic interchange reaction is anticipated to significantly impact the field of dynamic covalent chemistry, providing a versatile route for synthesizing a wide array of sulfur-containing heterocyclic compounds.