The team has studied the relationship between the ability of the coals to be dissolved in crude anthracene oil and their composition. The coal samples taken from different deposits in Russia and Mongolia were characterized by different stages of metamorphism and tested by the Fourier transform infrared spectroscopy and Carbon-13 nuclear magnetic resonance. The data of a correlation analysis enabled us to find out that an amount of aromatic structures in coal macromolecules provided the main influence on the thermal dissolution of the coals. The middle-rank coals had the highest rates of coal organic matter transfer to liquid products. The data showed that the dissolution process was accompanied by destruction of weak bonds among aliphatic groups. The amount of methylene groups in the aliphatic part of coal macromolecules had a direct impact on conversion of the coal organic matter into soluble products.