Unprecedented dioxygen-triggered oxidative radical process was explored using dioxygen as the solely terminal oxidant, realizing aerobic radical oxysulfonylation of unsaturated carbon-carbon bonds with high selectivity.β-Keto sulfones and secondary and tertiary β-hydroxysulfones could be obtained when using alkynes and alkenes as the starting materials respectively;Operando IR experiments revealed that pyridine not only as a base to successfully neutralize the sulfonic acids generated in situ but also plays vital roles in reducing the activity of sulfinic acids.