The molecular parameters of poly(vinyl alcohol) have enormous effects on its physical and chemical properties. Therefore, the surface characteristics of poly(vinyl alcohol) films are also determined by the molecular parameters. In this study, the dependence of the surface free energy on the molecular weight, degree of saponification, and stereoregularity of poly(vinyl alcohol) films has been evaluated with contact-angle measurements. The surface free energy of poly(vinyl alcohol) films increases with decreases in the syndiotactic dyad content, molecular weight, and degree of saponification. The polar component of the surface energy is not affected by the deviation of the molecular weight and degree of saponification very much. However, it decreases with increases in the syndiotactic dyad content and ranges from 11.64 to 4.35 dyn/cm. (c) 2007 Wiley Periodicals, Inc.