Films of polystyrene (PS) and poly(methyl methacrylate) (PMMA) blends of two different thicknesses have been examined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Blends with different compositions were spin-cast onto a mica substrate with chloroform as the mutual solvent. XPS measurements revealed surface enrichment of PMMA in all compositions. The thicker (66 nm) films exhibit a higher degree of PMMA surface enrichment than the thinner (17 nm) films. AFM imaging allows distinctions to be drawn between blends with differing compositions. The blend films with less than 50% PMMA bulk concentration generally exhibit pitted surfaces; the pit size varies with film thickness and bulk composition. When the PMMA bulk concentration is greater than 50%, the film surface changes to show island-like phase-separated structure. The surface segregation and morphology are explained in terms of solubilities of the two polymers in the solvent and dewetting of PMMA relative to PS. The phase domains on the film surface have also been resolved by frictional force microscopy (FFM) using hydrophilic tips bearing hydroxyl groups.