Abstract: In order to understand the effects of solvent pretreatment on the inherent macromolecular structure of low rank coal, Xilinguole lignite (XLL) and Shenfu sub-bituminous coal (SFC) were extracted by tetrahydrofuran (THF) soxhlet extraction, carbon disulfide/N-methyl-2-pyrrolidone (CS₂/NMP) mixed solvent extraction and thermal dissolution, respectively. The extracted coals were characterized by diffuse reflection FT-IR spectroscopy (DRIFT), thermogravimetric analysis (TGA), mercury intrusion method (MI) and swelling ratio determination. The results indicated that the extraction resulted in the arrangement and reassociation of coal inherent macromolecules. THF Soxhlet extraction and CS₂/NMP mixed solvent extraction can relax the macromolecular structure of coal to varying degrees by changing the non-covalent bond cross-linking, especially the distribution of hydrogen bond interactions. However, thermal dissolutions at high temperature mainly increased the covalent cross linking of coal macromolecules, especially for XLL. Swelling of all extracted coals was limited by Fickian diffusion, and the extracted coal showed lower swelling activation energy than the corresponding raw coals.