A spinnable mesophase pitch with 95 vol.% optical anisotropy and 267 °C softening point was prepared through co-polymerization of 95 wt.% naphthalene pitch and 5 wt.% C9 resin. The effects of introducing C9 resin on the formation, structure and properties of naphthalene-derived mesophase pitch and the oxidative stabilization of resulting pitch fibers as well as the final physical properties of carbon fibers were systematically investigated. The results suggest that C9 resin could effectively facilitate the generation and development of liquid crystals in synthetic naphthalene pitch during the heat soaking process and introduce a certain amount of methyl side chains linking in polycyclic aromatic hydrocarbon molecules, so as to reduce the melt viscosity of modified mesophase pitch and improve its flow-spinnability and oxidative reaction capability. The pre-oxidation process of the modified pitch-spun fibers could be completed ahead of 4 h at 240 °C in an air atmosphere, compared with unmodified pitch fibers. This shows a possibility to decrease the production cost of mesophase pitch-based carbon fibers. Although the tensile strength of 1000 °C carbonized fibers prepared from the modified mesophase pitch (1.23 GPa) is slightly higher than that of original carbon fibers (1.18 GPa), the axial electrical resistivity and the thermal conductivity of corresponding graphite fibers after 3000 °C graphitization are 2.0 μΩ m and 677 W/(m K), respectively, which are significantly enhanced in comparison with those of original graphite fibers (3.2 μΩ m and 473 W/(m K).