This invention provides an improved process for the preparation of chloroalkynes from alkynyl alcohols that comprises reacting an alkynyl alcohol with concentrated hydrochloric acid in the presence of anhydrous calcium chloride or calcium dichloride dihydrate and a copper catalyst to produce a chloroalkyne. The chloroalkynes can be employed to prepare alkynyl amines which are useful for the manufacture of biologically active materials. The present invention reduces the hazards of the chlorination reaction, eliminates or greatly reduces by-product formation, and provides certain environmental benefits.