We have developed a photoinduced transition-metal-free decarbonylative strategy at ambient temperature through non-covalent interactions to achieve vinyl sulfones. Traditionally, decarbonylative functionalization is accomplished using transition metal catalysts at elevated temperatures. The π-π interaction facilitates the elimination of CO to generate vinyl radical, thereby promoting the creation of C-S bonds with the sulfonyl radical. These interactions and the overall process were illuminated by spectroscopic investigations and mechanistic studies.