The efficient generation of 3-triflyloxyarynes, including those bearing a transformable group, through an iodine-magnesium exchange reaction of 1,3-bis(triflyloxy)-2-iodoarenes was achieved by using finely tuned reaction conditions that efficiently suppressed the competing thia-Fries rearrangement. The method enabled the facile synthesis of a wide range of multisubstituted arenes.