The surface compositions of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends have been investigated using x-ray photoelectron spectroscopy (XPS). The XPS results demonstrate that there are significant differences between the composition of the surfaces (e.g., outmost ∼6 nm) and the bulk of both miscible and immiscible blends. The surfaces of PS/PVME films dip-coated from either toluene or trichloroethylene solutions are found to be enriched in PVME. An additional enrichment in the PVME content of the surface is also observed when miscible PS/PVME blends are phase separated by heating them above the lower critical solution temperature. The average composition profile of a miscible 50/50(w) blend has been obtained by angular-dependent XPS measurements. This experiment suggests that the enrichment is the result of a concentration gradient rather than a monolayer coating. These results are discussed in terms of the surface free energies of PS and PVME and the degree of mixing in the surface layer.