Upper Freeport (Argonne Sample) coal was extracted with carbon disulfide-N-methyl-2-pyrrolidinone (CS2-NMP) mixed solvent at room temperature. The swelling behaviors for the raw coal, heavy extract fractions, and extraction residue were investigated in several organic solvents. The swelling ratio of the raw coal was lower than those of the extract fractions and residue, independent of the kind of solvents used. For both acetone-insoluble extract fraction and extraction residue, swelling ratio in THF increased with decreasing the sample/solvent weight ratio. The extract fractions and residue also showed similar swelling behaviors on effects of swelling time and temperature. These results suggest that the extraction residue has a similar cross-link structure as that for the extract fractions, i.e., a strongly associated structure among coal molecules through several noncovalent interactions, since the extract fractions seem to have little covalently bound cross-link structure as they are soluble in a better solvent such as the CS2-NMP mixed solvent. So, Upper Freeport raw coal also consists of mainly associated structure of coal molecules.