The thermal conductivity of 3D network reinforced polypropylene matrix composites was constructed by the pickering‐like emulsion method.

Polypropylene (PP) has the advantages of corrosion resistance, easy processing, and low dielectric loss, but its low thermal conductivity limits the application of its composites in fields such as electronic packaging. To solve this problem, in this work, composite microspheres with the segregated structure were prepared by coating boron nitride nanosheets (BNNSs) on the PP surface by Pickering‐like emulsion method, and BNNSs@PP composites with three‐dimensional thermal conductivity network were obtained after molding. Due to the high thermal conductivity of BNNSs and the formation of perfect thermal conduction pathways, the thermal conductivity of the composites reached 1.71 W m−1 K−1 when the content of BNNSs was 10.1 wt%, which was a 713% increase in thermal conductivity for that of pure PP. At the same time, the mechanical properties of the composites were ensured. This method provides a simple and effective technique to improve the thermal conductivity of PP‐based thermally conductive composites, which has a wide application potential in electronic packaging. [ABSTRACT FROM AUTHOR]