After administration of hexachlorobenzene rats excrete sulphur-containing conjugates from which pentachlorothiophenol can be split off. In the present study we describe the identification of pentachlorothiophenol and pentachlorothioanisol in the livers of animals treated with hexachlorobenzene. In order to clarify the further fate of these two substances, we administered them to rats, and isolated the conversion products excreted in the urine and feces. The metabolites of pentachlorothiophenol and pentachlorothioanisol are excreted in both conjugated and free form. From extracts of the excreta, we isolated tetra- and trichlorobenzene with two or three sulphur-containing substituents on the ring, analogous compounds in which thiol groups were converted into sulphoxide and sulphone groups, as well as analogous compounds with a phenolic oxygen in addition to sulphur, and sulphur-containing compounds in which clorine was replaced by hydrogen. Following administration of the sulphoxide and of the sulphone of pentachlorothioanisol under analogous conditions, pentachlorothiophenol and pentachlorothioanisol and their metabolites were detected in the excreta of the animals. No evidence was obtained that the parent compounds are excreted in the unchanged form.