Vinyl acetate was polymerized in ultraviolet-ray initiated bulk system at low temperatures using 2,2-azobis(2,4-dimethylvaleronitrile) (ADMVN) or 2,2-azobis(isobutyronitrile) (AIBN) as the photoinitiator, respectively. High molecular weight (HMW) poly(vinyl alcohol) (PVA) having number-average degree of polymerization ($P_n$) of 3,900-7,800 and syndiotactic diad (S-diad) content of 52.5-54.0% could be prepared by complete saponification of synthesized linear poly(vinyl acetate) (PVAc) having $P_n$ 5,900-9,400 obtained at conversion of below 30%. $P_n$ of PVA using ADMVN was larger than that of PVA using AIBN. On the other hand, conversion of the former was smaller than that of the latter, and it was found that the initiation rate of the ADMVN was lower than that of AIBN. This could be explained by a fact that the rate of photolysis of AIBN is faster than that of ADMVN due to the higher quantum yield or dissociation rate constant of AIBN than that of ADMVN. The $P_n$, syndiotacticity, and whiteness of PVA from PVAc polymerized at lower temperatures were superior to those of PVA from PVAc polymerized at higher temperatures.