Huangling coal is an important oil-rich coal resource in China. The rational and efficient utilization of oil-rich coal resources can not only promote China to reduce its dependence on coal and increase the use of clean energy, but also help China to achieve the goal of carbon peak and carbon neutrality. Therefore, ultrasonic-assisted extraction method was used to study the extraction of oil-rich Huangling coal by different extraction methods, and the molecular structure characteristics before and after extraction were analyzed by scanning electron microscopy, low-temperature liquid nitrogen adsorption method and Fourier transform infrared spectroscopy. The extraction effects of petroleum ether (PE), carbon disulfide (CS2), methanol (MeOH), acetone (DMK), carbon disulfide/acetone (CS2/DMK), carbon disulfide/nitromethyl pyrrolidone (CS2/NMP) under ultrasonic assisted conditions were investigated. The results show that the extraction rates of single-stage extraction are CS2/NMP, CS2/DMK, PE, DMK, MeOH and CS2 in descending order. The total extraction rate of PE, CS2, MeOH, DMK and CS2/DMK is 16.91%. The study on the structure of CS2/NMP extract and the fifth grade CS2/DMK extract show that the particle size of CS2/NMP extract decreases significantly, and the surface of the fifth grade CS2/NMP extract is loose and porous. The pore size and pore size of the fifth grade CS2/NMP extract at the pore size of less than 6 nm are higher than those of the fifth grade CS2/NMP extract. The aroma of CS2/NMP extract is higher than that of grade 5 extract. Compared with raw coal, the absorption peaks corresponding to fat structure and benzene ring 4 substitution of the two kinds of raffinate are obviously weakened, and the characteristic absorption peaks of minerals are significantly strengthened and the aliphatic chain is longer and branched chain was reduced, indicating that these two extracts are more conducive to oil formation.