Described is a process for separating an organic phase comprising mainly propyl bromide from a crude reaction mixture formed by free-radical catalyzed hydrobromination of propylene with hydrogen bromide. The process comprises (A) feeding cold water into an upper or mid-portion of a packed column; (B) concurrently feeding the crude reaction mixture into an upper portion and/or mid-portion of the column so that the water contacts the crude reaction mixture; to form a mixture of (i) an acidic aqueous phase comprising aqueous hydrogen bromide and (ii) an organic phase comprising propyl bromide; (C) withdrawing the resultant phases from said column, at a rate comparable to the feeds being made into the column; and (D) separating the phases to form an upper acidic aqueous phase comprising aqueous hydrogen bromide superposed on a lower liquid organic phase comprising propyl bromide, and separating these upper and lower phases from each other.