In this work, thermally conductive yet electrically insulative polycarbonate (PC)‐based composites with hybrid boron nitride (BN) and flake graphite (Gt) network structure were prepared by high shear injection molding process. A synergy in improving the thermal conductivity of PC was observed with the hybrid loading of BN and Gt. Results showed that the in‐plane thermal conductivity of PC/BN 30 wt%/Gt 16 wt% composite reached as high as 4.08 W/mK, which were 189% and 358% higher than that of PC/BN 30 wt% and PC/Gt 16 wt% composites, respectively. The preferred orientation of planar fillers and interconnection between added fillers were indispensable to the significant increase of in‐plane thermal conductivity, as corroborated by X‐ray diffraction, rheology and scanning electron microscope observations. Moreover, the electrical resistivity of PC/BN 30 wt%/Gt composites was higher than 1014 Ω cm, which shows potential application in thermal management areas such as advanced electronic devices and battery units among others.