Films of polystyrene (PS) and poly(methyl methacrylate) (PMMA) blend have been annealed at a temperature above their glass transition temperatures for up to 48 h. Surface chemical compositions of the cast and annealed films were measured by X-ray photoelectron spectroscopy (XPS) while surface topographical changes were followed by atomic force microscopy (AFM). The blend films spin-cast from chloroform produce nonequilibrium surfaces with a significant excess of PMMA. The polymer component with a lower surface free energy, PS, is shown to segregate to the surface upon annealing. The PS surface concentration of the films, containing 50% PS:50% PMMA in the bulk, was evaluated using the ester peak in XPS C Is spectra (sampling depth similar to9 nm) and found to increase from similar to5% (freshly spin-cast film) to a saturated level of similar to 47% after 17 h of annealing. AFM imaging reveals evolution of blend morphology with annealing time. The spin-cast films prior to annealing exhibit pitted topography with typical pit size of similar to1.2 mum and depth of 30-40 nm. As the annealing process proceeds, these pits get continually shallower. Frictional force microscopy with hydroxylated tips recorded surface phase separations for the films of 2-4 h annealing. As the annealing continues to above 14 h, the pitted structure becomes distorted. The surface enrichment and morphology changes upon annealing are explained by dewetting of PMMA relative to PS.