The scientific value of biaryls is easily recognized from the broad utilization of these compounds as versatile building blocks for functional materials such as liquid crystals, or ligands for metal catalysts and pharmaceuticals since the structures are frequently seen in natural products. Of the synthetic methods of biaryls, oxidative coupling reaction of arenes is the most ideal one reducing the number of synthetic steps and production of wastes. However, the usual methods still have limited applications owing to the difficulty in obtaining cross-coupling products, because undesired homocoupling dimers are formed. In this symposium, we report a novel oxidative cross-coupling between two unfunctionalized arenes using hypervalent iodine(III) reagents as the oxidants. The key aspect of the reaction is the selective single-electron oxidation ability of hypervalent iodine(III) reagents toward arenes to produce the corresponding cation radical intermediates.