To precisely identify the effect of blend ratios of syndiotacticity-rich poly(vinyl alcohol) (s-PVA)/atactic PVA (a-PVA) on the water stability of s-PVA/a-PVA/iodine complex blend films, we prepared two PVAs with similar number-averaged degrees of polymerization of 4000 and degrees of saponification of 99.9% and with different syndiotactic diad contents of 58.5 and 53.5%, respectively. The desorption behavior of iodine in s-PVA/a-PVA/iodine complex films in water was investigated in terms of the solubility of s-PVA/a-PVA blend films in water. The degree of solubility of s-PVA/a-PVA blend films with s-PVA content over 50% in water at 70degreesC was limited to about 10-20%, whereas that of s-PVA/a-PVA blend films with s-PVA content of 10% was 85% under the same conditions. The degree of iodine desorption of complex blend films decreased with increasing s-PVA content. The degree of iodine desorption of s-PVA/a-PVA drawn film with s-PVA content of 90% was limited to 7%, regardless of the soaking temperature from 30 to 70degreesC. The desorption of iodine in water was strongly affected by the dissolution of blends. Moreover, the stability of iodine in the drawn s-PVA/a-PVA/iodine blend films in hot water was far superior to that of the undrawn film. (C) 2004 Wiley Periodicals, Inc.