To study the chemical composition change of the extracted coal in different macrolithotype, the cocking coal samples were taken from the Pingdingshan coal fields, and the extract solution of tetrahydrofuran (THF), carbon disulfide (CS2) and acetic acid (HAc) were experimentally conducted on the samples in this paper. Based on the chromatography and fourier transform infrared spectroscopy (FTIR), coal solution-extraction rate, chemical component and major functional group changes were investigated. The study find extraction yield of organic solvents on the vitrain is the highest, followed by the clarian, the durian, among different lithotype of coal. Further, the extraction yield of CS2 is the highest and THF is relatively higher than HAc. The hydrocarbon contents in the extraction decrease in the sequence of the vitrain, the clarian, and the durian, whereas the non- hydrocarbon components increase correspondingly. More bituminic is extracted from the coal sample under THF extraction, but more saturated hydrocarbon is done under CS2 extraction. Further comparison of function group between the pre-extracted coal and the pro-extracted coal of the same sample, fatty hydrocarbon content and oxygenic functional groups of the vitrain are the highest, the fat structure parameter is the largest, the aromatization of the coaland the proportion of aromatic to the fatty hydrocarbon are the smallest, while the durian has the largest proportion of aromatic to the fatty hydrocarbon. In addition, in all the solutions treated to the coal, the fatty hydrocarbon and oxygenic functional groups in the pro-extracted coal decrease in different degrees, the vitrain is the most obvious, whereas the aromatization of the durian residue and the proportion of aromatic to the fatty hydrocarbon are the largest. In these cases, oxygen-containing functional group can be significantly extracted by CS2, while the hydrogen-bond hydroxyl, phenols groups and fatty hydrocarbon are dramatically extracted by THF.