A differential scanning calorimetry (DSC) study on the extraction residues of coals giving different extraction yields (which were prepared by changing the solvent composition of a carbon disulfide-N-methyl-2-pyrrolidinone mixed solvent extraction) was carried out. For the residues from Upper Freeport coal (APCS-1) with extraction yields lower than 30 wt % (daf), an endothermic peak similar to that given by the raw coal was observed around 350 degrees C. This endothermic peak disappeared on the second and third scans, indicating that the peak is due to irreversible structural changes in coals. For the residues from the high extraction yield experiments, the peak was not observed up to 400 degrees C, even during the first scan. The reason for these endothermic peaks was discussed from the relationship among the extraction, swelling, and structural changes of coals.