Vinyl acetate (VAc) was solution-polymerized in tertiary butyl alcohol (TBA) and in dimethyl sulfoxide (DMSO) having low chain transfer constant at 30, 40, and 50 degreesC, using a low temperature initiator, 2,2'-azobis(2,4-dimethylvaleronitrile) (ADMVN). The effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl acetate) (PVAc) and corresponding poly(vinyl alcohol) (PVA) obtained by saponification with sodium hydroxide. The polymerization rates of VAc in TEA and in DMSO were proportional to the 0.49 and 0.72 powers of ADMVN concentration, respectively. For the same polymerization conditions, TEA was absolutely superior to DMSO in increasing the molecular weight of PVA. In contrast, TEA was inferior to DMSO in causing conversion to polymer, indicating that the initiation rate of VAc in TEA was lower than that in DMSO. These effects could be explained by a kinetic order of ADMVN concentration calculated using initial rate method and by an activation energy difference of polymerization obtained from the Arrhenius plot. Low-temperature solution polymerization of VAc in TEA or DMSO by adopting ADMVN proved successful in obtaining PVA of high molecular weight (number-average degree of polymerization (P-n): 4100-6100) and of high yield (ultimate conversion of VAc into PVAc: 55-80%) with diminishing heat generated during polymerization. In the case of bulk polymerization of VAc at the same conditions, maximum P-n and conversion of 5200-6200 and 20-30% was obtained, respectively. The P-n and lightness were higher, and the degree of branching was lower with PVA prepared from PVAc polymerized at lower temperatures in TEA.