Abstract Poor interfacial adhesion between carbon fibers (CF) and the resin matrix has been a limiting factor in advancing the properties of composites. To address this challenge, this study employs the sizing method to coat carbon nanotubes (CNTs) and hexagonal boron nitride nanosheets (h‐BN) onto the CF surface. The 3D structures formed by strategic of combination 1D and 2D nanomaterials, markedly enhances the mechanical, thermal and frictional properties of CF composites. The results reveal a significant boost in the flexural strength, flexural modulus, interlaminar shear strength and interfacial shear strength of the prepared CF composites, registering increases of 53.96%, 60.41%, 55.58% and 55.35%, respectively. These advancements stem from the heightened surface reactivity and roughness of the fibers, facilitated by the synergistic interactions between CNTs and BN. Furthermore, the thermal conductivity of the composites exhibits a remarkable increase of 63.56%, attributed to the synergistic coupling between CF and BN, establishing an efficient thermal conductivity pathway within the composites. This research provides a highly effective approach for crafting high‐performance CF composites. Highlights Construction of 3D network structures on CF surfaces by the sizing method. Synergistic coupling between BN and CNT enhances composite properties. Synergistic enhancement of friction and thermal properties of CF composites.

Construction of 3D nanostructures on carbon fiber surfaces by sizing for preparing high‐performance composites