CP/MAS C-13 NMR analyses have been made for different frozen solutions of poly(vinyl alcohol) (PVA) samples with different tacticities to obtain further information about the intramolecular hydrogen bonding of PVA. Aqueous or deuterated dimethyl sulfoxide (DMSO-d(6)) solutions (3 wt %) have been frozen in a rotating MAS rotor by cooling to -50 degrees C. The CH resonance lines of the frozen PVA solutions split in different ways, significantly depending on the tacticities and the solvents. These CH resonance lines can be well resolved into six to eight constituent lines by the least-squares method, whose lines have different chemical shifts evaluated by assuming the downfield shifts due to the intramolecular hydrogen bonding and the upfield shifts induced by the gamma-gauche effect. Furthermore, the relative intensities of the lines thus resolved are successfully interpreted for the frozen atactic PVA solutions by the statistical treatment assuming the statistical formation of the intramolecular hydrogen bonds and the random distribution of the trans and gauche conformations along the PVA chains. The probabilities of the trans conformation and the intramolecular hydrogen bond are also determined through this analysis for atactic PVA samples. In contrast, such calculations based on Bernoullian statistics cannot be applied to the cases of the frozen isotactic PVA solutions, suggesting that certain specific conformations are preferably formed for the isotactic PVA samples.