Abstract: Pullulan forms an association complex with PEG in a hydrous system. The assocation complex, as well as its pullulan and PEG components, exerts a decreased solubility in water. The association reduces or even eliminates the excessively high water-solubility, threading and stickiness of pullulan so that this extends the uses of pullulan and PEG such as those in gradually disintegrable- and sustained release-shaped articles for consumer's products, toiletries, cosmetics, pharmaceuticals and feeds.