Phenols are the important high value-added chemical product of coal tar, and exploring the release behavior of phenols is crucial for clarifying the coal pyrolysis mechanism and regulating the product distribution. The aim of this paper is to investigate the effects of swelling on the pyrolytic properties of de-ashed vitrinite (VD) and de-ashed inertinite (ID). VD and ID prepared by Shendong coal were characterized by 13C NMR, XPS and FTIR to explore physicochemical properties. Acetic acid (AA), ethanol (EA) and acetone (AT) were employed to prepare the swelled VD (VD-AA, VD-EA and VD-AT) and swelled ID (ID-AA, ID-EA and ID-AT). Kinetic analysis was carried out using thermogravimetry, the pyrolysis characteristics and distribution of pyrolysis products were analyzed by fast pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS) and fast pyrolysis fixed bed. Combining with density functional theory (DFT), the possible pyrolysis pathways of phenols generation were proposed. As a result, the macromolecular structures of VD and ID are constructed. TG and kinetic analysis exhibit that swelling promotes the pyrolysis of VD and ID, and the activation energy of the second stage is VD > VD-EA > VD-AT > VD-AA and ID > ID-EA > ID-AT > ID-AA, respectively. Py-GC/MS analysis exhibits that the selectivity of phenol, cresol, xylenol and catechol decreases to 17.53 % (VD-AA) and 12.18 % (ID-AT). By analyzing and comparing the distribution of the full component of Py-GC/MS, seven possible pathways of cresol generation are proposed. DFT calculation exhibits that Path 3 of VD-AT, which produces cresol via sequential decarboxylation, ether bond cleavage, decarbonylation, aliphatic side chain removal and dehydroxylation, demonstrates the lowest reaction energy of −148.38 kJ/mol.