Sulfone skeletons have widespread applications in many fields and therefore convenient methods for the synthesis of sulfones are highly desirable. However, as a direct approach towards sulfone skeletons with commercially available feedstock styrenes, alkynylsulfonylation of vinylarenes is still a challenge. Herein, a metal-free, two-component alkynylsulfonylation of vinylarenes under mild conditions has been developed. Various vinylarenes and aryl alkynylsulfones are reliable substrates to afford the corresponding β-sulfonyl alkynes in moderate to excellent yields. Synthetic applications of the products have also been demonstrated.