The miscibility and surface crystalline structure of blends containing poly(vinylidene fluoride) (PVDF) composed of alpha and gamma phases were investigated by atomic force microscopy (AFM) and differential scanning calorimeter (d.s.c.) measurements. It was found that the surface crystalline phase of PVDF and the degree of surface enrichment of a lower surface free energy component in a blend might strongly be affected by the magnitude of the intermolecular interaction, even though the blend is miscible. Also, the segmental interaction parameters was determined by combining the T-m depression of PVDF in a blend and the binary interaction model. According to the binary interaction model, the introduction of a carboxyl group for miscible [poly(methyl methacrylate)/PVDF] and [poly(vinyl acetate)/PVDF] blends decreased their miscibility.