Coal liquefied residue is the common byproduct from the coal liquefaction process, and accounting for about 30 wt% of the coal [1, 2]. It’s a kind of solid material with high contents of carbon, sulfur, and ash. Traditional utilization of coal liquefied residue were combustion, gasification, rammed-coal coking, and so on [3, 4]. However, there is no obvious improvement in economic efficiency of currently utilization of coal liquefied residue. Researchers [3, 5–9] found that some organic solvent (toluene, tetrahydrofuran, and coking washing oil) have a strong solubility on coal liquefied residue. Using the method of solvent extraction–hot filtration–distillation can obtain coal liquefied pitch (CLP) with high contents of carbon (more than 88 wt%), low sulfur, and scarcely any ash. CLP is a good precursor to produce high-quality carbon/graphite materials. For example, Hu’s group [10–12] and Qiu’s team [13–18] have successfully produced carbon foam and porous carbon materials with the CLP as the raw material. These new carbon materials have been well applied to environmental materials and energy materials. Zhou [19] has reported that, the CLP is a key material to produce carbon microfiber. CLP is also a desired raw material to produce needle-coke with the high aromaticity and low ash [20]. On the other hand, CLP has an extremely high softening point and viscosity, which leads a distinctly difficulty on the deep processing. Liquid-phase carbonization is the most common method to produce high-quality coal-based carbon material. Thus in, it’s crucial in detailed analysis on the changes in structure of CLP during liquid-phase carbonization process.