The reaction of poly(vinyl chloride) containing N-methyl dithiocarbamate (PMD) with metal ions in a heterogeneous system and the effect of γ-irradiation on the reactivity were studied. PMD powder suspended in aqueous solutions did not show any reactivity toward metal ions. However, the PMD powder suspended in a methyl alcohol solution formed a chelate with various metal ions. The effects of the reaction time, pH, and the initial concentration of the metal ion were examined. PMD irradiated in methyl alcohol with γ-irradiation doses up to 28 Mrad was compared with the original PMD. The reactivity of the irradiated PMD toward the metal ions did not show any apparent decrease.