Incorporating intelligent materials in concrete allows for self-sensing capabilities by reflecting the concrete’s strain and tensile status through the electrical properties. In order to enhance the self-diagnostic abilities of intelligent concrete, we conducted research on how intelligent materials affect the fracture mechanics of concrete. This study examines the fracture mechanical properties of the carbon nanofiber cement mortar and paste based on three-point bending and nanoindentation tests. The results showed that the carbon nanofiber content has negligible influence on the crack initiation toughness of the specimens. However, the instability toughness exhibited an initial increase followed by a decrease as the carbon nanofiber content increased. At a fiber content of 0.2%, the crack initiation toughness improved maximally by 13.1% compared to the control group. At a fiber content of 0.5%, both the ductility index and fracture energy increased with the nanofiber content, improving by 84% and 66.3%, respectively. The incorporation of carbon nanofibers did not alter the composition of cement paste hydration products; the fracture toughness of each hydration product varies from 0.14 to 0.59 MPa·m1/2. However, the fracture toughness of individual hydration products and un-hydrated particles is higher than the macroscopic three-point bending fracture toughness values of the specimens.