On an industrial scale, barium chloride is prepared via a two step process from barite (barium sulfate). The first step requires high temperatures.
The second step requires reaction between barium sulfide and hydrogen chloride:
or between barium sulfide and calcium chloride:
In place of HCl, chlorine can be used. Barium chloride is extracted out from the mixture with water. From water solutions of barium chloride, its dihydrate () can be crystallized as colorless crystals.
Barium chloride can in principle be prepared by the reaction between barium hydroxide or barium carbonate with hydrogen chloride. These basic salts react with hydrochloric acid to give hydrated barium chloride.