Vinyl pivalate (VPi) was solution-polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) with low chain transfer constant using a low temperature initiator, 2,2'-azobis(2,4-dimethylvaleronitrile) (ADMVN). TEA was absolutely superior to DMSO in increasing the syndiotacticity and molecular weight of poly(vinyl alcohol) (PVA). Low-temperature solution polymerization of VPi in TEA or DMSO by adopting ADMVN proved to be successful in obtaining PVA of ultrahigh molecular weight (maximum number-average degree of polymerization (P-n): 13,500-17,000) and of high yield (ultimate conversion of VPi into PVPi: 55-80%) to a much higher conversion than that from bulk polymerization. Moreover, PVA from TEA system were fibrous, with a high degree of orientation of the crystallites, indicating the syndiotactic nature of TEA polymerization.