The paper presents an iron-catalyzed cross-electrophile coupling reaction that couples benzyl halides with disulfides to form thioether products. This reaction is unique in that it does not require a terminal reductant or photoredox conditions, and it avoids sulfur-induced catalyst poisoning or the use of exogenous bases. The method is versatile and can be applied to a wide range of substrates, including benzyl halides and disulfides with various functional groups and aryl substituents. The authors demonstrate the generality of the reaction through extensive substrate scope studies and highlight its potential in gram-scale synthesis, drug synthesis, and bioconjugation. Mechanistic studies reveal that the reaction proceeds via an Fe(0) oxidative cleavage event between iron and the (pseudo)halide substrate, with thioethers being active reagents in the process. The study also explores the application of this reaction in the synthesis of biologically active molecules, such as sulfoxides, sulfones, and thiols, and its utility in cleaving cysteine-derived disulfides for bioconjugation. Overall, the iron-catalyzed cross-electrophile coupling reaction offers a new and efficient approach to the synthesis of thioether products, with potential applications in various fields including pharmaceuticals and materials science.The paper presents an iron-catalyzed cross-electrophile coupling reaction that couples benzyl halides with disulfides to form thioether products. This reaction is unique in that it does not require a terminal reductant or photoredox conditions, and it avoids sulfur-induced catalyst poisoning or the use of exogenous bases. The method is versatile and can be applied to a wide range of substrates, including benzyl halides and disulfides with various functional groups and aryl substituents. The authors demonstrate the generality of the reaction through extensive substrate scope studies and highlight its potential in gram-scale synthesis, drug synthesis, and bioconjugation. Mechanistic studies reveal that the reaction proceeds via an Fe(0) oxidative cleavage event between iron and the (pseudo)halide substrate, with thioethers being active reagents in the process. The study also explores the application of this reaction in the synthesis of biologically active molecules, such as sulfoxides, sulfones, and thiols, and its utility in cleaving cysteine-derived disulfides for bioconjugation. Overall, the iron-catalyzed cross-electrophile coupling reaction offers a new and efficient approach to the synthesis of thioether products, with potential applications in various fields including pharmaceuticals and materials science.