Coal pitch mainly consists of aromatic hydrocarbons, phenolic substances, and aliphatic hydrocarbons, the macromolecular structures formed by these cyclic and chain hydrocarbons through chemical bonding possess diversity and complexity. In this study, medium- and low-temperature coal tar pitch (LCTP) served as the primary material for the production of mesophase pitch via co-carbonization with hydrogenated tail oil (HTO). Aimed to clarify the effects of different amounts of HTO addition and analyze the mechanism of introducing naphthenic and aromatic hydrocarbons on the liquid phase carbonization process. When HTO additive amount is 30%, the carbonized product with the largest content of mature graphite crystals at 25.01%, and the smallest degree of defects. The analytical mechanism demonstrates that the condensation of naphthenic hydrocarbons introduced by HTO produces hydrogen radicals, the hydrogen transfer reaction saturates a significant quantity of free radicals generated within the system, thereby impeding further rapid condensation and curing, and decreasing the viscosity of the system. On the other hand, the aromatic hydrocarbons introduced undergo dehydrogenation and condensation to produce additional polycyclic aromatic hydrocarbons, thereby contributing to a more abundant carbon structure conducive to the development of mesophase pitch. The combined effect of aromatic hydrocarbons and naphthenic hydrocarbons facilitates the slow development of the mesophase structure into a broad-area optical structure. This study provides an effective method for improving the performance of coal-based mesophase pitch, which reduces the production cost and promotes the clean and high value-added utilization of limited resources.