AbstractTwo‐dimensional (2D) MXene (MX) and silane coupling agents are increasingly used to modify carbon materials for the fabrication of composite functional materials, which exhibit enhanced electrical, optical, and mechanical properties due to the synergistic effects of both MX and silane. We demonstrate the modification of carbon fibers (CFs) with MX and three different kinds of silane coupling agents, including 3‐aminopropyltriethoxysilane, 3‐glycidyloxypropyldimethoxymethylsilane, and 3‐mercaptopropyltriethoxysilane, which are named as CF‐MX@N, CF‐MX@O, and CF‐MX@S, respectively, and further prepare the CF‐MX@silane/epoxy (EP) composites. The utilized silane coupling agents serve as bridges between MX and CFs, forming CF‐MX@silane composites. Through comparative analysis, it is found that the CF‐MX@S composites form a strong interface phase through covalent bonds, significantly enhancing the interface compatibility and revealing strong interface adhesion. The interfacial shear strength of the molded CF‐MX@S/EP composites increases to 119.7 MPa, with an 173.9% enhancement comparing to unmodified composites. This work can offer useful guidance and reference for selecting appropriate silane coupling agent to modify CFs with 2D materials to form high‐performance composite materials.Highlights Silane coupling agents are used as bridges to graft MXene‐modified CFs The surface modification of CFs is achieved by a simple one‐step approach Excellent interfacial phase is constructed through forming strong covalent bonds Microstructure and failure interface are responsible to interface strengthen.