Polymerizations of N-carboxy anhydrides of L-phenylalanine, γ-benzyl-L-glutamate, O-carbobenzoxy-L-tyrosine, L-leucine, and sarcosine, as initiated by primary, secondary, and tertiary amines in N2or CO2atmospheres and in the presence or absence of NaH, indicate that they proceed via carbamate salt intermediates. This conclusion is supported by radiotracer studies as well as by NMR studies of the initial products of NCA-amine reaction mixtures.