Benziodoxole triflate (BXT), a cyclic iodine(III) electrophile, has been found to promote a rearrangement of propargylic alcohols into alpha,beta-unsaturated ketones bearing an alpha-lambda(3)-iodanyl group. This iodo(III)-Meyer-Schuster rearrangement proceeds under mild conditions and tolerates a variety of functionalized propargylic alcohols, thus complementing previously reported halogen-intercepted Meyer-Schuster rearrangement. The alpha-lambda(3)-iodanylenones can be utilized for facile Pd-catalyzed cross-coupling for the synthesis of multisubstituted enones.