Epoxy resin (EP) composites are attracting intensive interest for aviation aircraft applications due to superior machinability and high corrosion resistance. However, the poor tribological performance of EP matrix greatly limits its wide application because of highly brittle and weak thermal properties. Herein, we constructed a vine-like [email protected]2/Carbon nanofiber aerogel (MMoCA) via directed freezing method and cellulose carbonization treatment. The obtained MMoCA exhibited long-range-aligned 3D porous lamellar structure and the [email protected]2 attached to carbon nanofiber surface presented good dispersion inside the aerogel. Such a novel aerogel bestowed the EP composites with outstanding thermal properties through constructing continuous oriented thermal diffusion channels inside the EP matrix. Meanwhile MMoCA reinforced EP composites (MMoCA-EP) showed great potential in tribological application, resulting from the rapid friction heat dissipation and high-quality transfer films during the friction process. This study has a significant guidance to develop high performance polymer composites in the frontier field of tribology.