The surface enrichment of blend films of poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) cast from various solvents has been investigated by contact angle, X-ray photoelectron spectroscopic and attenuated total reflection Fourier transform infra-red spectroscopic measurements. The composition of each component was fixed at 50 wt%. The surfaces of miscible PMMA/PVAc blend films are found to be enriched in PVAc regardless of casting solvents. It was found that the surface enrichment of PVAc in the PMMA/PVAc blend is reduced when the as-cast blend film shows phase separation or when the phase-mixed blend is heated above the lower critical solution temperature and exhibits thermally induced phase separation.