With the growing challenges of modern electronics in heat dissipation, developing thermal management materials with high thermal conductivity and electrical insulation property remains an important issue for electronics. In this work, a novel three-dimensional network (3D) of boron nitride/reduced graphene oxide (BN/rGO) with covalent bond connections were fabricated by using the surface modification and ice-templated methods. The as-prepared boron nitride/reduced graphene oxide/nature rubber composites (BN/rGO/NR) possessed an enhanced through-plane thermal conductivity of 1.28 W m−1 K−1 and satisfactory electrical insulation at a low filler loading of 4.9 vol%. The results demonstrated that the covalent bond connections and three-dimensional networks of fillers greatly reduced the interfacial thermal resistance as well as phonon scatterings at the filler/filler and filler/matrix interface simultaneously. More importantly, this strategy provided a creative insight to the design of advanced thermal management materials and also presented a bright application prospect for next-generation electronic packing. BN and rGO were connected by the covalent bonds through using the surface modified method. BN/rGO/NR composites were fabricated by the ice-templated and vacuum-assisted method. Display omitted