The surface free energy per unit area of a solid, ␥ S , is a fundamental property of materials and determines their surface and interfacial behavior in processes like wetting and adhesion. In this study the ␥ S of a series of styrene-acrylonitrile random copolymers is evaluated. Three different approaches are used to determine the components in which the surface free energy can be decomposed. Using the geometric and the harmonic mean approach, the dispersive, ␥ d , and polar, ␥ p , components of the solid surface free energy were determined and compared to the Lifshitz-van der Waals, ␥ LW , and acid-base, ␥ AB , components using the approach developed by C. J. van Oss et al. (1987, Adv. Colloid Interface Sci. 28, 35). The acid-base approach was also used to evaluate the work of adhesion of the test liquids: water, glycerol, and thiodiglycol. It was found that the contact angles of these liquids follow closely the predictions of Cassie equation. The evaluation of the surface free energy components on one hand and the relative magnitude of the work of adhesion components on the other hand, suggest that below 50% of acrylonitrile the polystyrene repeating units are preferentially at the surface. Above 50% of acrylonitrile the segregation of the low-energy homopolymer at the surface decreases.