A new type of organocatalyzed 1,3-thiosulfonylation has been developed to straightforwardly access highly functionalized vinyl sulfones, which features mild conditions, atom- and step-economy, practicability, conciseness, and environmental friendliness. Moreover, these valuable products can be transformed to vinyl sulfides via a base-promoted isomerization. The versatile route can efficiently and rapidly introduce SCD3 groups with excellent levels of deuterium content (>99% D) by utilizing our newly developed SCD3 reagents. Gram-scale operations and further transformations are smoothly carried out, providing promising applications for drug discovery.