AbstractReactive organosulfenyl chlorides (ArSCl) or selenenyl chlorides (ArSeCl), generated in situ from the reaction of PhICl2 with diorganyl disulfides or diselenides, enable the intramolecular oxidative cyclization/chalcogenylation of β,γ-unsaturated oximes, leading to the formation of a series of chalcogenylated isooxazolines in good to excellent yield.