Pyridine extraction of coal can separate the small molecules from macromolecule skeleton and subsequently impacts the thermal behavior of coal. A perhydrous bituminous coal with a high content of volatile matters was extracted by pyridine under microwave irradiation with an extraction yield of 24.6% on the dry, ash free basis (daf). The thermal behavior of the raw coal, its extract and residue was investigated by thermogravimetric analysis and in-situ Fourier Transform Infrared Spectroscopy (FTIR) based on the evolution of weight loss and functional groups, respectively. Though pyridine extraction had only slight effect on TG curve of the perhydrous coal, it greatly influenced the evolution of functional groups during pyrolysis. Aromatic C-H and C=O was the most susceptible to pyridine extraction because the absence of extractable moieties reduced the production of radicals and the reactions between small molecules and macromolecules during pyrolysis. The interactions between extractable small molecules and non-extractable macromolecules could retard the decomposition of aromatic C=C and hydroxyls. The evolution of aliphatic groups and C-O was slightly impacted due to the occurrence of the abundant aliphatic side groups and bridge bonds in macromolecule structures. (C) 2018 Energy Institute. Published by Elsevier Ltd. All rights reserved.