The configurational assignment of poly(vinylpyrrolidone) (PVP) prepared by peroxide-initiated solution polymerization was studied by the combination of one- and two-dimensional NMR spectroscopy. The broad and overlapping H-1-NMR and C-13{H-1}-NMR spectra of PVP were assigned to the configurational triad, pentad (CH, (CH2)-C-2, (CH2)-C-3, and (CH2)-C-4 regions), and tetrad (beta-CH2 region) sequences. The configurational assignments of the various carbon resonances were confirmed with the help of two-dimensional experiments such as heteronuclear single quantum correlation (HSQC), heteronuclear single quantum correlation-total correlation spectroscopy (2-D HSQC-TOCSY). The various geminal and vicinal couplings within the configurational sequences were assigned with the help of total correlation spectroscopy (TOCSY low mixing time). The propagation pathway was studied using the C-13{H-1}-NMR (carbonyl carbon) and N-15{H-1}-NMR spectra, The N-15{H-1} resonance signals were assigned to pentad-level configurational sequences. The results obtained by the analysis of the area under the resonance signals confirmed that poly(vinylpyrrolidone) obeys Bernoullian statistics,