It was found that CCl4 can add to linear and cyclic olefins and dienes in the presence of manganese, vanadium, and molybdenum complexes. The effects of the olefin nature, temperature, reaction time, the nature of the catalyst central atom, and its ligand environment on the reaction selectivity and on the yields of tetrachlorinated derivatives were studied. The addition of primary alcohols to the vanadium- and molybdenum-containing catalysts facilitated a decrease in the reaction temperature to 125-150degreesC, which was due to the oxidation of alcohols with CCl4 to alkyl hypochlorites, which act as coinitiators of CCl4 addition to alkenes.