Abstract A new and highly efficient vicinal thiosulfonylation of 1,1‐dibromo‐1‐alkenes with thiosulfonates in the presence of cesium carbonate has been developed. The metal‐free diheterofunctionalization is an operationally simple to access a wide range of ( E )‐1,2‐thiosulfonylethenes (α‐aryl‐β‐thioarylvinyl sulfones) in moderate to high yields with high levels of stereoselectivities. Further, scalable reactions have been demonstrated for this transformation, thus illustrating its efficiency and practicality. magnified image