A visible-light-induced intermolecular sulfur-alkenylation of alkenes, including both activated and unactivated alkenes, is described. This sulfur-alkenylation reaction proceed in a highly regio- and stereospecific manner involving the visible-light-induced conversion of a ketene dithioacetal to the thiavinyl 1,3-dipole intermediate, followed by a formal [3 + 2] cycloaddition and C-S bond cleavage. Furthermore, it is also an efficient approach for the late-stage functionalization of natural products and complex molecules, even being induced by sunlight under ambient conditions.