Hexachlorobutadiene reacts with thioalcohols (2-mercaptoethanol, 4-mercapto-1-butanol and 6-mercapto-1-hexanol) in aqueous ethanol in the presence of sodium hydroxide to give the new thioethers 1,2,3,4,4-pentachloro-1-(2-hydroxyethylthio)-1,3-butadiene, 1,2,3,4,4-pentachloro-1-(4-hydroxybutylthio)-1,3-butadiene and 1,2,3,4,4-pentachloro-1-(6-hydroxyhexylthio)-1,3-butadiene. The hydroxy groups of these products are converted to chlorides with SOCl2 in pyridine. New long chain sulfides were synthesized by reaction of the S-substituted polychloro-1,3-butadienes with thiols (ethyl-, 2-hydroxyethyl-, propyl- and butyl-) in the presence of sodium ethoxide in ethanol. Furthermore, hexachlorobutadiene gave new S- and -S,S-substituted polychloro-1,3-butadiene derivatives with 2,3,5,6-tetrafluorobenzenethiol and 2,4-difluorobenzenethiol in aqueous ethanol in the presence of sodium hydroxide or in DMF in the presence of triethylamine. The structures of the new compounds were characterized by microanalyses and spectroscopic data.