The potassium t-butoxide-catalyzed ring-opening polymerization of 3,3-dimethyl- and 4,4-dimethyl-2-azetidinone proceeds quantitatively in a mixture of N,N-dimethylacetamide and 5-10 wt % of lithium chloride at 25 degrees C to give the corresponding monodisperse polyamides. The addition of methyl alpha-D-glucoside into the living polyamide system gives a novel polyamide linked with the glucose moiety at one chain end. A new graft copolymer composed of a water soluble polysaccharide (dextran) backbone and many monodisperse polyamide branches was also prepared by a similar coupling method. The difference in acidity among the lactam monomers, the corresponding polyamides, and the alcohols was essential for the attainment of such a proton transfer-controlled system composed of the living polymerization and the subsequent coupling reaction.