In this study, vinyltriethoxysilane (TEVS) was introduced onto the surface of carbon fiber using liquid-phase oxidation and impregnation methods to incorporate vinyl groups onto the carbon fiber, thereby enhancing the chemical bonding between the carbon fiber and norbornene–polyimide (PI-NA). Through a systematic study of the hydrolysis conditions and concentration of the TEVS solution, the optimal modification conditions were determined. These conditions were used to graft TEVS onto the surface of oxidized carbon fiber to prepare carbon-fiber-reinforced PI-NA composites (CF/PI-NA). The results show that when carbon fiber was treated with a 0.4 wt% TEVS solution, the interlaminar shear strength (ILSS) of the composites reached 65.12 MPa, and the interfacial shear strength (IFSS) reached 88.58 MPa, representing increases of 27.58% and 35.62%, respectively, compared to the CF/PI-NA composite materials prepared from untreated carbon fiber. It is worth noting that the modification method described in the study is simple and easy to implement, and it has the potential for large-scale continuous production applications.