Styrene-co-acrylonitrile (SAN) copolymers were prepared by the emulsion polymerization with different AN content, which were blended with poly(vinylidene fluoride) (PVDF). DMA results show that, with increase of the AN content, Tg of PVDF phase shifts to higher temperature. XRD tests indicate that PVDF shows the α phase and the variation of AN content in SAN has no influence on the α phase in PVDF/SAN blends. PVDF shows the double melting behavior and the crystallization temperature of PVDF shifts to lower temperature with increase of AN content. Torque test shows the viscosity of PVDF is high and the addition of SAN induces decrease of viscosity of the blends. Contact angle test shows the hydrophilicity of PVDF improves with the addition of SAN.