Abstract: Due to the easy-processing, high permittivity and low filler loading, the demand of polymer/conductive fillers dielectric (PCD) materials has experienced a significant increase in the past decade. According to the micro-capacitor model, when the concentration is close to the percolation threshold, the permittivity would have a significant improvement. However, the dramatic decline in breakdown strength may limit the applications. In order to solve these problems, prior work had been dedicated to controlling the dispersion of nanoparticles, with the aim of promoting molecular polarization and cutting off the direct contact of fillers. Nevertheless, it was difficult to precisely control the dispersion, direct contact of fillers seems to be inevitable. Thus, through controlling the distribution of fillers to completely cut off the conductive path may be a considerable method. In this work, multilayer co-extrusion technology was used to fabricate the dielectric samples with alternating multilayered structure. One of the layers in the specimen was pure poly(vinylidene fluoride) (PVDF), and its adjacent layer was PVDF composite filled with 15wt% carbon black (CB). Polarized optical micrographs showed that the layer structure was still stable even when the number of layers reached 64. Crystallization peaks observed from DSC curves demonstrated that more layers tended to induce a better distribution of CB. The results obtained from dielectric tests displayed that when the number of layers was increased from 2 to 64, the permittivity engaged an order of magnitude improvement accompanied with the increase of the dielectric loss which led to a distinct enhancement of EMI shielding efficiency from 19 to 38dB. The absorption of electromagnetic wave was regarded as the main contribution to the improvement of EMI shielding. ACKNOWLEDGMENTS: The authors are grateful to the financial support of National Natural Science Foundation of China (51203097, 512278106).