Fusain from Tongting (Huaibei, Anhui Province) bituminous (FTTB) coal was fractionally extracted using Soxhlet extractor with CS2. Then the extracts were analyzed with GC/MS. Comparison of experimental data between FTTB coal and clarain from Tongting bituminous (CTTB) coal was carried out. The results show that the kinds of small molecule components detected by GC/MS of FTTB are less than those of CTTB. Long-chain alkanes exist mostly in the extracts of fusain. Macromolecular networks are predominant in the FTTB coal mainly composed of inertinite in the coal petrography. The size of micropores in the FTTB coal is relatively small, and the development of micropores is relatively low. Thus the content of aromatic compounds with affinity for micropores is relative low in FTTB, while the content of long-chain alkanes with affinity for macromolecule networks is relatively high. Sub-components in exinite determine the distribution of long-chain alkanes extracted in the last stage. Odd-numbered carbon distribution appears when resin is most in exinite, while high carbon alkane distribution appears when exinite is dominant in cutinite. Small aromatic molecules are firstly packed in micropores, and exist in a free state after micropores are saturated.