A gold-catalyzed sulfonylation of aryl/vinyl iodides to synthesize aryl sulfones facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis was developed. In the reaction, aryl sodium sulfinates or sulphinic acids can react smoothly with aryl/vinyl iodides to directly construct various aryl sulfones. The strong synthetic capabilities of sulfone synthesis are demonstrated by its easily available and handled reagents, good functional group compatibility, and late-stage application of complicated biomolecules. Mechanistic studies suggest that the silver salt plays a crucial role in the transmetalation with the Au(I)/Au(III) intermediate, and the gold complex favors Au-S bond formation over Au-O bond formation.