Poly(vinyl acetate)(PVAc) was obtained via emulsion polymerization of vinyl acetate at various conditions, and then poly(vinyl alcohol)(PVA) having maximum number-average degree of polymerization ($P_{n}$ ) of 3,600 was prepared by saponifying PVAc having of 14,000~15,000 and degree of branching for acetyl group of about 3~3.5 polymerized at 5$0^{circ}C$ with concentrated alkaline aqueous solution. Syndiotactic dias content and crystal melting temperature of PVA slightly increased with a decrease in the polymerization temperature and the syndiotactic diad content and crystal melting temperature for PVA polymerized at 5$0^{circ}C$ were about 49~50% and 229$^{circ}C$C, respectively, independently of PVA.