The thermal decomposition reactions of Ni(OH)Cl.l½H20 in still air and in nitrogen and β-CO2(OH)3Cl and γ-Cu2(OH)3Cl in nitrogen atmosphere, have been studied by DTA and TG analysis, and the intermediates and final products have been characterized by x-ray diffraction and infrared spectroscop. The thermal evolution ot the above indicated compounds under dynamic vacuum conditions has be en studied with the aid of an x-ray high teaperature diffraction chamber. They reveals that in these conditions, the pure metallic nickel, copper and cobalt can be obtained at comparative low temperature. The infrared spectra of thése hydroxychlorides have been tentatively assigned