Sulfur dioxide (SO2) is a gaseous environmental pollutant which is routinely used in industry as a preservative and antimicrobial. Recent data suggests that SO2 may have value as a therapeutic agent. However, due to its gaseous nature, localizing SO2 generation is challenging. Herein, various 1,3-dihydrobenzo[c]thiophene 2,2-dioxides (benzosulfones) were prepared as candidates for photochemically activated sulfur dioxide (SO2) generation. These compounds were found to be stable in buffer but were photolysed upon irradiation with UV light to generate SO2. Our data indicates that photolysis of benzosulfones depends on substituents, and that the presence of electron donating groups results in an enhanced yield of SO2.