The reactions of several gem- and vic-polychloroethanes containing 3–5 Cl atoms with PhONa in dimethyl sulfoxide and with PhSNa in N,N-dimethylformamide were examined. Either the mono-, di-, or tetra-substituted compounds of polychloroethylenes were obtained as the main products, depending on the kinds of substrates as well as on the amounts of the bases. The reaction products from polychloroethylenes