To commercialize a degradable material, it is necessary to control the initial stability which is strongly depended on their life time. One approach to modify physical properties of degradable polyesters is a blend with a non-degradable polymer because a non-degradable polymer with low surface energy is enriched at surface. Biodegradable polyesters, such as poly(dl-lactide) (dl-PLA), semi-crystalline poly(l-lactide) (l-PLA) and poly(epsilon-caprolactone) (PCL) were blended with poly(vinylidene fluoride) (PVDF) as a non-degradable polymer because PVDF has a low surface energy. Their surface structure and morphology were measured by X-ray photoelectron spectrometer and atomic force microscopy, respectively. (dl-PLA/PVDF) and (PCL/PVDF) blend films showed the enrichment of PVDF at surface whereas the surface of (l-PLA/PVDF) blend film was similar with its bulk one due to different solubilities to solvent and miscibility. These results will be useful to control of the initial stability of degradable polymers.