The tacticity of poly(vinylamine) (PVAm) prepared from tert-butyl N-vinylcarbamate (PVAmI) and from N-vinylacetamide (PVAmII) was determined by 13C NMR. The configurational sensitivity was optimal at pH 8.8, where nine well-resolved methine carbon resonances and five methylene carbon resonances were observed. Based on the meso (m) and racemic (r) assignments for the methylene carbon resonances of PVAm made previously by the use of heteronuclear correlated 2D NMR experiments, the diad distribution for the PVAmI methylene regions was found to be 56% (r) and 44% (m). These results were extended to the tetrad analysis of the methylene peaks. The triad analysis was obtained from the relative area of the three distinct methine regions. The pentad assignments were made by a comparison of the nine methine peak areas with those calculated from first-order Markov and Bernoullian statistics. This analysis is supported, at the triad level, by 15N NMR. Acetylated PVAmI, poly(N-vinylacetamide), was characterized by 1H NMR for triad analysis of the COCH3 group. This analysis gave internally consistent results with the 13C analysis. A similar analysis for PVAmII gave 49% (r) and 51% (m). © 1986, American Chemical Society. All rights reserved.