We report the preparation of nanostructurecl adaptive polymer surfaces by diffusion of an amphihilic block copolymer toward the interface. The surface segregation of a diblock copolymer, polystyrene-block-poly(acrylic acid) (PS-b-PAA), occurred when blended with high molecular weight polystyrene employed as a matrix. On annealing, the polymer surfaces changed both the chemical composition and the hydrophilicity depending on the environment and pH, respectively. By exposure to either water vapor or air, the surface wettability varied between hydrophilic and hydrophobic. In addition, surface enrichment on diblock copolymer by water vapor annealing led to self-assembly occurring at the interface. Hence, nanostructured domains can be observed by AFM in liquid media. Moreover, the PAA segments placed at the interface respond to pH and can switch from an extended hydrophilic state at basic pH values to a collapsed hydrophobic state in acidic media. Accordingly, the surface morphology changed from swelled micelles to nanometer size holes. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2982-2990, 2010