β-keto-sulfones are an important sulfone-containing molecules and also serves as a versatile building blocks in organic synthsis. In this paper, we developed a novel method to construct various β-keto-sulfones that formed from the radical sulfonylation of carbonyl α-Csp3-H. The present method in-cluding two steps: firstly, the ketones react with DMF-DMA to generate more reactive enaminone inter-mediate, then with the assistance of FeCl3?6H2O/TBHP system, the enaminone intermediate underwent radical addition, oxidation, nucleophilic substitution and the loss of DMF would produce the β-keto-sulfones. This methodology will provide new strategies for construct β-keto-sulfone-type products, which has advantages of simple operation, mild reaction conditions and good functional group tolerance.