With eEmploying dichloromethane as solvent, sodium dodecanesulphonate as surface active agent, ammonium persulphate as oxidizer, PAn was introduced into PVDF and co-polymer with high relative permittivity reaching to 280 was obtained by emulsion polymerization. By detecting the structural information and electrical property through FT-IR, XRD, SEM, informations about the co-polymers were presented and in this paper. By adjusting the quantity of aniline in polymerization and the concentrations of protonic acid in the post processing, polymers with different electric properties could bewere compared and analyzed. It was The SEM images and XRD patterns showed the crystallization and microstructure information of the co-polymers in comparison. Particularly, the SEM images showed that the PVDF-PAn co-polymers had homogeneous properties in certain constitute range and as a result of emulsion, spherical PAn-PVDF media was fabricated. After robber mixing procedure at certain temperature, the PAn had a relatively average-fine dissolving in the PVDF, which overcame the difficulty of dissolving PAn oin other substrateance. This ensured the fine property for the matrix material in composites. The XRD pattern showed, wWith the increasing of the introduction quantity of PAn, the crystallization of the entire material complex had been raised greatly.