Poly(vinyl alcohol) (PVA) resins with various alcoholysis degrees (78%~93%) were synthesized and cast into films, and the influence of alcoholysis degree on the various properties of PVA films was investigated. Differential scanning calorimetry (DSC) testing revealed a positive correlation between the alcoholysis degrees and melting point as well as crystallinity of the PVA films. Furthermore, the tensile property tests indicate that the higher the alcoholysis degrees is, the greater the tensile strength and elongation at break of PVA films are. Intriguingly, the dissolution time of the PVA films exhibits an inverted U-shaped pattern, with the films having an alcoholysis degree of 86%~88% exhibiting the most optimal water-soluble properties.