Simple operation, easily accessible starting materials, and short syntheses of the privileged scaffold thiochromane 1,1-dioxide that widely exist in bioactive molecules was achieved by photocatalytic divergent cyclization of α-allyl-β-ketosulfones with arylsulfonyl chlorides. Optimization and scope and limitations of this short and general pathway are described. The methodology provides an efficient strategy for the construction of a wide variety of thiochromane 1,1-dioxide derivatives.