The feasibility of catalytic chlorination of adamantane and its derivatives by carbon tetrachloride in the presence of manganese-, vanadium-, and molybdenum-containing catalysts activated by nitrile ligands or alcohols was established. The optimum molar ratios of catalyst components and reactants and the optimum reaction conditions for selective syntheses of mono-, di-, and trichlorosubstituted adamantane derivatives with high yields were found.