In‐depth understanding of coal conversion processes is a key step for clean and efficient utilization of coals in chemical industry. Currently, most analytic methods aim to evaluate heteroatom release on the entire molecules. However, the production of value‐added chemicals from complex mixtures like coals are technically demanding which inevitably requires in‐depth fundamental knowledge of the treatment processes for coals. In‐source collision‐activated dissociation (ISCAD), a mass spectrometric method, can obtain details of aromatic cores and was employed in this work to provide in‐depth understanding of the catalytic conversion process of a low‐rank coal under different solvent conditions. Different heteroatom release patterns on aromatic and alkyl locations were observed for the solvents. Each solvent exhibited a characteristic preference over deoxygenation/denitrogenation on aromatic versus alkyl positions. Such preference is important for developing a desired catalytic treatment for a targeted heteroatom release. Overall, this study provides novel insights in catalytic heteroatom release processes during coal conversion that may be critical for the production of value‐added chemicals from coals.