Contact angles of water on stereoregular poly(methyl methacrylate)s (PMMA) solvent-cast in the form of films against a glass substrate were measured by using the sessile drop method. The syndiotactic films exhibited contact angle values indicative of relative dominance of the nonpolar alpha-methyl and methylene groups of polymer chains at the air-side surface and the polar ester groups at the glass-side surface of the films. The selectivity in the surface exposure of functional groups increased rapidly with syndiotacticity. On the contrary, the wetting results for the isotactic films showed no effect of the polarity of contacting medium on the surface chemical composition and the wettability of the films represented an average for alpha-methyl, methylene, and eater groups both at the air-side and at the glass-side surface. The observed influence of tacticity on the surface activity of stereoregular PMMAs was interpreted in terms of the surface conformational structure of these materials.