Abstract: High-temperature thermal extraction (TE) of Xianfeng lignite by different solvents was carried out, and FT-IR spectra of extracts and residues were determined. The results indicate that Xianfeng lignite shows the macro-molecular network structure by chemical bond cross-linking, in which some low molecular compounds are associated by non-covalent interaction. The TE can distinctly increase the extraction yields, which are up to 20.7% and 21.3% at 300℃ in toluene and tetralin, respectively. The extracts result from the release of low molecular compounds by thermal rupture of non-covalent bonds at high temperature. Meanwhile, there is no obviously pyrolysis in the process of thermal extraction at 300℃. So the hydrogen donor solvent and hydrogen bond solvent can not increase the thermal extraction yield. The thermal extracts of Xianfeng lignite contain a great of aliphatic alkyl and carbonyl ester, a little of hydroxyl and aromatic structure. The solvent of thermal extraction shows distinctly influences on the constitution and structure of extracts.