The structure and hydrogen bonding of the melt-crystallized atactic poly(vinyl alcohol) (A-PVA) films, which were carefully prepared without significant thermal degradation, have been charactefized by CP/MAS C-13 NMR spectroscopy. The C-13 spin-lattice relaxation analysis has revealed that there exist three components with different T-1C values, the crystalline, less mobile noncrystalline and mobile noncrystalline components, in good accord with the results for different PVA samples previously reported. It should be noted that the T-1C values of the crystalline and noncrystalline components are appreciably smaller for the melt-crystallized films than those for the un-annealed and annealed samples prepared by casting from the aqueous solution. The C-13 NMR spectra of the crystalline and noncrystalline components are separately recorded by using the difference in T-1C and their CH lines are successfully resolved into three and seven constituent lines by the least-squares curve fitting. respectively. Moreover, the statistical analysis of the integrated intensities of the Constituent lines thus obtained enables to determine the probability f(a) for the formation of intramolecular hydrogen bonding in the successive two OH groups along each chain and another probability f(t) of the trans conformation for the crystalline and noncrystalline components. It is found that theft, value is relatively larger for the melt-crystallized films than those for the un-annealed and annealed samples. On the basis of these results, the features of the melt-crystallization and the resulting crystalline-noncrystalline structure are discussed by particularly considering effects of intra-and inter-molecular hydrogen bonding on the crystallization. (c) 2006 Elsevier Ltd. All rights reserved.