5-(Methacryloyloxy)methyl-1,3-oxathiolane-2-thione (3) was synthesized from glycidyl methacrylate (GMA) and carbon disulfide in the presence of lithium bromide in 93% yield. The radical polymerization of 3 in DMSO initiated by AIBN at 60 degrees C afforded corresponding polymethacrylate 4 quantitatively. Copolymerization of 3 with MMA was also carried out. 5-Phenoxymethyl-1,3-oxathiolane-2-thione (6), model dithiocarbonate, reacts with benzylamine at room temperature to afford 0-(1-mercapto-3-phenoxy-2-propyl)N-benzyl-thiocarbamate (7) and 1,1’-dithiobis[3-phenoxy-2-(benzylaminothiocarbonyloxy)-propane] (8) in 89% and 7% yield, respectively. Polymer 4 reacted with butylamine or dipropylamine to afford a corresponding polymethacrylate bearing thiol group, which immediately turned to insoluble gel by facile auto-oxidation of the thiol group.