The present work enhanced the thermal conductivity of poly(p-phenylene sulfi de)/expanded graphites and poly(p-phenylene sulfi de)/carbon nanotubes, by incorporating composites with hexagonal boron nitride, which simultaneously succeeded in raising the electrical conductivity of the systems. A two-step mechanical processing method which includes rotating solid-state premixing and inner mixing was adopted to improve dispersion of the hybrids, contributing to the formation of an interspered thermal conductive network. Similar synergic effect in thermal conductivity enhancement was discovered in the hybrid systems regardless of the dimension difference between the two carbon fi llers. Such is postulated to be the one satisfying advantage generated by the afore-mentioned network; the other is the insulativity of the hybrid systems given by the effective blockage of hexagonal boron nitride as an insulating material in our network. The present work enhanced the thermal conductivity of poly (p-phenylene sulfi de) / expanded graphites and poly (p-phenylene sulfi de) / carbon nanotubes, by incorporating composites with hexagonal boron nitride, which pairs succeeded in raising the electrical conductivity of the systems. A two-step mechanical processing method which includes rotating solid-state premixing and inner mixing was adapted to improve dispersion of the hybrids, contributing to the formation of an interspered thermal conductive network. Similar synergic effect in thermal conductivity enhancement was discovered in the hybrid systems regardless of the dimension difference between the two carbon fi llers. Such is postulated to be the one satisfying advantage generated by the afore-mentioned network; the other is the insulativity of the hybrid systems given by the effective blockage of hexagonal boron nitride as an insulating material in our network.