Abstract: The graphene nanoplates (GNPs) were used as a type of conductive filler and coated onto the surface of polyphenylene sulfide (PPS) granules through high-speed mixing, and then the PPS/GNPs composites with a segregated structure were fabricated by compression molding. The morphology, electrical properties and electromagnetic interference shielding performance of the composites were investigated by use of optical microscope, scanning electron microscope, electrometer and vector network analyzer. The results indicated that there was a perfect segregated structure formed within the composites. With such a segregated structure, the composites exhibited outstanding electrical conductivity and electromagnetic interference shielding effectiveness (EMI SE). The composites achieved an electrical conductivity of 25.6 S/m and a high EMI SE of 41.0 dB when 3.0 wt% GNPs was incorporated.