A novel copper-catalyzed cross-coupling of arylsulfonyl radicals with diazo compounds is described for the synthesis of various arylsulfones under mild conditions. In this reaction, the cheap, environmentally friendly, and readily available inorganic K2S2O5 is employed as the sulfur dioxide source for providing arylsulfonyl radicals. In addition, a radical mechanism involving the insertion of sulfur dioxide with aryl radicals followed by the coupling of arylsulfonyl radicals with copper carbenes is proposed.