A novel and highly efficient I2/K2CO3 mediated regioselective sulfonylation of thiophenols, aryl acetylenic acid and aromatic alkynes with N-hydroxy sulfonamide has been developed. N-hydroxy sulfonamide has been used for the first time for the synthesis of these sulfones. The scope and versatility of the reaction has been demonstrated by the regio- and stereoselective synthesis of different analogs of sulfones with various structural features.