Sulfidated nano- and microscale zero-valent iron (S-(n)ZVI) has shown enhanced selectivity and reactive lifetime in the degradation of chlorinated ethenes (CEs) compared to pristine (n)ZVI. However, varying effects of sulfidation on the dechlorination rates of structurally similar CEs have been reported, with the underlying mechanisms remaining poorly understood. In this study, we investigated the -dichloroelimination reactions of tetrachloroethene (PCE), trichloroethene (TCE), -1,2-dichloroethene (-DCE), and -1,2-dichloroethene (-DCE) at the S and Fe sites of several S-(n)ZVI surface models by using density functional theory. Dechlorination reactions were both kinetically and thermodynamically more favorable at Fe sites compared to S sites, indicating that maintaining the accessibility of reactive Fe sites is crucial for achieving high S-(n)ZVI reactivity with contaminants. At Fe sites adjacent to S atoms, the reactivity for CE dechlorination followed the order -DCE ≈ TCE > -DCE > PCE. PCE degradation was hindered at these sites due to the steric effects of S atoms. At the S sites, the energy barriers correlated with the CEs' energy of the lowest unoccupied molecular orbital in the order PCE < TCE < DCE isomers. Our findings reveal that the experimentally observed selectivity of S-(n)ZVI materials for individual CEs can be explained by an interplay of the varying reactivities of Fe and S sites in CE dechlorination reactions.