Photoredox alkene or alkyne alkylsulfonylation has been achieved with phthalimide esters and sulfinates providing unexpected α-sulfones. Mechanistic studies disclose that the preferential alkyl radical addition to the alkene or the Markovnikov hydrosulfonation of the alkyne should contribute to the formation of the β-alkylated α-sulfones. Moreover, the reaction is easy to operate covering quite large substrate scales including primary, secondary and tertiary alkyl groups and all sorts of terminal aryl alkenes or alkynes. Besides, the reaction was also suitable for the sulfonylation of several drug molecules.