To the best of our knowledge, there is no method for vicinal thiosulfonylation of ynones has been disclosed to date. Therefore, the development of novel and mechanically different method for vicinal thiosulfonylation of ynones is highly desirable. As part of our continuous research on C-S bond formation reactions, we envisaged that a base can catalyze the Michael-addition/nucleophilic substitution tandem reaction of ynones and thiosulfonates to produce multifunctional vinylsulfones through a novel non-radical process. Herein, we would like to report this result.