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Skeletal editing has rapidly established itself as a transformative platform for accessing structural diversity from preexisting molecular scaffolds, circumventing the need for de novo synthesis. Among atom‐level alterations of molecular cores, atom swap stands out by allowing programmable ring deformation through the precise exchange of atoms. However, the effective remodeling of heterocyclic frameworks through S‐to‐N atom exchange has remained virtually unexplored. We now disclose the first example for skeletal editing of benzodithiol‐3‐ones via S‐to‐N atom swap, which not only provides a direct and efficient route to the pharmaceutically relevant benzo[ d ]isothiazol‐3(2 H )‐one scaffold but also unveils a novel nitrene‐mediated ring reconstruction. More details are discussed in the article by Yang et al . on pages 3621—3628. image