Heat removal via thermal management materials is attracting more and more attention in the electronic industry. Conventional particle/polymer thermal conductive composites require a high filler loading ratio (>30 vol %), which cause severe thermal interfacial resistance and mechanical issue. In this work, we fabricate tellurium nanowires (NWs)/epoxy nanocomposites via a facile bar coating method. According to Agari model and Maxwell–Eucken model, the as‐synthesized ultra‐long NWs with high aspect ratio (>100) construct the 3D interconnected thermal conductive network better in resin matrix to facilitate the heat transfer process. The results show that at a low loading ratio of 2.4 vol %, this nanocomposite exhibits the out‐of‐plane and in‐plane thermal conductivity of 0.378 and 1.63 W m−1 K−1, respectively, which is 189 and 715% higher than that of pure epoxy resin. Importantly, good stability, and flexibility of nanocomposites are well maintained. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47054.

Ever‐increasing packaging and power densities of modern electronic devices in the present “More‐than‐Moore” technology era demand higher performance thermal interface materials (TIMs). However, conventional composite TIMs require higher loading to achieve better thermal conductive property, resulting in a mechanical problem. The poor wetting property of matrix loading materials further increases the interfacial thermal resistance (ITR). In this work, a one‐step hydrothermal method is employed to grow 2D molybdenum disulfide (MoS2) nanosheets on a tellurium (Te) nanowire skeleton and silver (Ag) nanoparticles are further decorated on MoS2 nanosheets via the photoreduction method. The in‐plane thermal conductivity of the final nanocomposite reaches as high as 10.4 W m−1 K−1, which is 4,160% higher than that of a pure epoxy resin and one order of magnitude higher than that of conventional polymeric nanocomposites. The 3D interconnected heat transferring network of Te/MoS2/Ag greatly enhances the thermal stability of the composite in practical applications. The rational materials design concept may contribute to the development of new types of high‐performance thermal management materials.