The recent progress of non-covalent associative structure of coal, and the mechanisms of the CS2/NMP (1:1 by volume) mixed solvent and the additive addition enhancing the extraction yield of coals were reviewed, and the aggregation behavior of coal in solid and solution states were presented, and the aggregation behavior of coal in solid and solution states were introduced in this paper. Coal extraction and swelling in organic solvents at room temperature were the most useful methods to understand the associative structure of coal. CS2/NMP (1:1 by volume) is a unique solvent to give high extraction yields for some bituminous coals. Some additives can dissociate the stronger interactions among coal molecules and enhance the extraction yields of coal in the mixed solvent.