A CuBr 2 -catalyzed annulation of 2-bromo-N-arylbenzimidamide with selenium/sulfur powder for the synthesis of benzo[d]isoselenazole and benzo [d]isothiazole in generally good yields was investigated. This synthetic strategy features good substrate scope and functional group tolerance. Furthermore, the corresponding products could be converted into N-aryl indoles via rhodium III -catalyzed ortho C−H activation of the N-phenyl ring, providing an efficient approach for axial aromatic molecules.