The dependence of surface structure of the poly(vinylidene fluoride) (PVDF)/poly(methylmethacrylate) (PMMA) films by solution casting on properties of seven substrates was investigated by wide angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR), scanning electron microscope (SEM) and differential scanning calorimetry (DSC). It was revealed that the polyblend films obtained by casting onto each substrate contained exclusively beta phase PVDF. Higher crystallinity of the film was obtained by casting onto ceramic, polytetrafluoroethylene (PTFE), copper (Cu), stainless steel and glass substrates than that by casting onto aluminium (Al) and polypropylene (PP) substrates, depending on the degree of close lattice matching. The surface crystalline structure of PVDF was strongly affected by the wettability of substrate. The largest size of PVDF spherulitic crystal structure with about 6 mu m presented in the casting film grown at the air/solution interface on glass substrate, while the smallest spherulite size with about 3 mu m was generated by casting onto PTFE, stainless steel and PP substrates. It implied that the higher surface tension the substrate had, the larger PVDF spherulite grew at the air/solution interface. (C) 2007 Elsevier B.V. All rights reserved.