The desorption behavior of iodine in syndiotactic poly(vinyl alcohol) (s-PVA) with a syndiotactic diad content of 63.1%; iodine film in water was investigated in relation to the solubility of s-PVA in water. Despite a low number-average degree of polymerization of 900, the degree of solubility of s-PVA film in water at 80 degreesC was limited to about 10%, whereas atactic poly(vinyl alcohol) (a-PVA) film was completely soluble at a lower temperature, 50 degreesC. The degree of iodine desorption of s-PVA/iodine film at a high temperature decreased remarkably compared with that of a-PVA/iodine film. The fastness of iodine of the drawn s-PVA/iodine film was far superior to that of the undrawn film. Over a draw ratio of 5, the iodine desorption was suppressed significantly with increasing drawing temperature rather than the draw ratio. In addition, the iodine desorption of postdrawn s-PVA/iodine film was lower than that of predrawn s-PVA/iodine film.