Provided is a new process useful for preparing arylsulfonyl halides, which comprises the addition or drowning of halosulfonation reaction products, produced by the reaction of aromatic compounds (arenes), with excess halosulfonic acid, into C.sub.3 -C.sub.6 aliphatic ketones, preferably acetone, isopropyl alcohol, or mixtures thereof, instead of drowning into water as is known in the art of aromatic sulfonyl chloride preparation. Less heat of reaction is observed, thus making the drowning of the halosulfonation reaction mixture safer and more controllable. Further, less hydrogen chloride gas is evolved from the drowning mixture and generally more highly pure arylsulfonyl chlorides are produced.