To prepare a syndiotactic poly(vinyl alcohol) (PVA)/gold complex for various biomedical applications, ultrahigh-molecular-weight syndiotactic PVA microfibrils were directly prepared by the saponification of poly(vinyl pivalate) that was obtained through bulk polymerization of vinyl pivalate at 30degreesC. PVA microfibrils with a number-average degree of polymerization, syndiotactic diad content, and degree of saponification of 14,300, 61.7%, and 99.9%, respectively, were gold-coated by sputtering at 140 and 150 W (Watt) for 1, 2, and 3 min, respectively. A weight gain of up to 7% by the gold atoms for the PVA microfibrils treated at 150 W for 3 min was found. Morphological changes at the surface were observed by a microscopic method. A mechanism of gold coating on PVA microfibrils is suggested. (C) 2003 Wiley Periodicals, Inc.