Poly (vinyl acetate)-PVAc and poly (vinyl alcohol)-PVA derived therefrom has been prepared by means of radiation induced emulsion polymerization as well as chemically initiated. The structure and properties of PVAc and PVA obtained by both methods are compared. It was found that PVAc prepared by radiation polymerization has lower 1, 2-diol content, higher degree of crystallinity, lower solubility in water, higher steel-steel adhesive strength, higher glass transition temperature and so on. Results of experiments showed some structure-property relationship of PVAc and PVA. For example, the solubility of PVA is mainly dependent on its crystallinity, which depends on the 1,2-diol content. The T,g, and adhesive strength also depend on the degree of branching and molecular weight, respectively.