Efficient heat dissipation is becoming a key limiting factor for the next‐generation smart electronic devices with ever‐increasing power density. The thermal interface materials (TIMs), with high out‐of‐plane thermal conductivity (TC) and excellent mechanical properties, are thus highly desired. In the present work, an elastomer‐type TIM is fabricated with silicone rubber (SR) as the matrix, and 3D interconnected graphene aerogel (gGA) as the nano‐filler. The lattice defects of graphene are remarkably repaired by graphitization at over 2800 °C, probably with chemical covalent bonding between the graphene sheets, so as to decrease the interfacial phonon scattering. What is more, the results of X‐ray diffraction and Raman spectroscopy confirm the thorough reduction and defects repair of 3D continuous graphene network, which can accelerate the heat dissipation. By vacuum/pressure alternate assisted impregnation, the as‐obtained gGA/SR composites show a consolidate structure with superior mechanical flexibility, which is desirable for TIMs. The TC reaches up to 1.26 W m^？1 K^？1 at a very low gGA loading of 0.50 wt%, which is 448% higher than that of pure SR (0.23 W m^？1 K^？1). This indicates that the 3D crossed‐ed graphene aerogel is an effective scaffold for enhancing the heat dissipation performance of advanced thermal management materials.

Here, inspired by welding, we proposed a simple way to prepare a high thermal conductive 3D continuous network by high-temperature treatment (2800 °C). We developed a simple and effective method to prepare gGA/SR composite as TIM. In the composite, 3D continuous graphene work with high TC was designed and prepared by high-temperature graphitization, which presumably convert the van der Waals force into chemical covalent bonding between the inter sheets. The TC of gGA/SR reached 1.26 W W m^？1 K^？1 (an increase of 448%) at a low loading of graphene (only 0.5 wt%). The TC enhancement of per wt% graphene is as much as 896%. The high TC and excellent mechanical performance endow the composite bright potential applications as TIMs.