A unique copper-catalyzed binucleophilic switching of 2-aminopyridine has been developed for the regioselective synthesis of 2- and 3-iodoimidazo[1,2-a]pyridines using alkenes/alkynes as coupling partners in the presence of molecular iodine under aerobic reaction conditions. This method was also applied to the synthesis of 2-iodo-3-phenylbenzo[d]imidazo[2,1-b]thiazoles. This protocol offers an easy route towards the synthesis of 2,3-diarylimidazo[1,2-a]pyridines.