Some basic physical properties, structure and hydrogen bonding have been characterized for different stereoregular PVA films including highly isotactic PVAs (HI-PVAs), which were recently succeeded in synthesis, as functions of the mm fraction by using different analytical methods. The melting temperature, degree of crystallinity, and C-13 spin-lattice relaxation time of the crystalline component are found to have their own clear minima at the mm fraction of about 0.4-0.5. This fact suggests that structural disordering associated with the decrease in crystallinity may be most strongly induced at this mm fraction. The formation of the new crystal form of PVA has been reconfirmed for HI-PVAs with the mm fractions higher than about 0.55 by FTIR spectroscopy and the structure and hydrogen bonding have been investigated in detail by solid-state C-13 NMR spectroscopy. It is found that all OH groups are allowed to form successive intramolecular hydrogen bonding along the respective chains in the crystalline region for HI-PVAs with the mm fractions higher than about 0.7. Since these chains should contain some amount of r units even in the crystalline region, a slightly helical structure with a considerably long period may be adopted by them as an energetically stable state. On the basis of the line shape analysis of the CP/MAS C-13 NMR spectra of the crystalline components, structural causes of the appearance of the minima of the physical values described above are also discussed in relation to the introduction of disordered units mainly associated with hydrogen bonding to the syndiotactic or isotactic sequences forming successive intermolecular or intramolecular hydrogen bonding, respectively. (c) 2006 Elsevier Ltd. All rights reserved.