Designing ordered fillers arrangement and superior interfacial adhesion between fillers and matrix can improve the thermal conductivity (TC) of composites. Here, bioinspired dopamine chemistry was firstly used to reduce graphene oxide (GO) and introduce polydopamine nanoparticles on the surface of GO. Then, a well-aligned epoxy/reduced GO films (EP/RGFs) nanocomposites were prepared via the simple vacuum impregnation. Compared with the random distribution of fillers in a traditional blending composite, fillers were selectively distributed in matrix and continuous thermal conductive network structures were constructed in this strategy. As a result, the nanocomposite exhibited a high TC of 0.913 W m?1 K?1 which is 4.8 times higher than pure EP. In addition, curing kinetics showed that RGFs were similar to an amine-type curing agent that reacted with EP and bonded them tightly, and its nanocomposites reaction activation energy is lower than that of pure EP. These results indicated RGFs possessed excellent interface compatibility with EP and suppressing effectively the phonon scattering at the EP–RGFs interface. Cooling experiments showed that nanocomposites can reduce by about 10 °C for a hot source (80 °C), demonstrating it can transfer efficiently heat energy from the heat source. This study provides an effective method for the preparation of high-performance thermal management composites.