A strategy for sulfonylation of boronic acids with sulfonyl chlorides has been established via Suzuki‐type radical cross‐coupling. This approach allows for the synthesis of more than 50 sulfone examples enabled by photoredox catalysis under visible light radiation. Moreover, the title reaction is successfully applied in late‐stage functionalization of bioactive molecules, and further transformation of the resulting sulfones into 2‐functionalized sulfones, borates, triphenylphosphine oxide and N‐arylcarbazole can be also achieved.