The previous results indicated that the bonding strength between graphene and carbon fiber (CF) has a greater impact on the reinforcement efficiency. And chemical bonding can provide the maximum bonding force between graphene and CF, which usually requires a series of complicated processes and a long preparation time. In this research, we have established a direct and efficient method to manufacture Graphene/CF hierarchical reinforcement based on chemical bonding. The Graphene/CF hierarchical reinforcement was prepared by the means of the rapid insertion and addition reaction of diaryl carbene. FTIR, Raman, XPS, XRD confirmed the structure of graphene and CF. Graphene-modified multi-scale composites exhibit excellent comprehensive properties, including ILSS (97.2 MPa), flexural strength (2043 MPa) and Tg (240 °C), which are increased by 23.2%, 34.4%, and 13 °C, respectively. This protocol was considered to provide an alternative strategy for the rapid and large-scale manufacturing of graphene/CF hierarchical reinforced materials based on covalent bonds.