We used X-ray photoelectron spectroscopy (XPS) to examine structural changes in the chemical form of nitrogen in coal induced by thermal extraction with organic or industrial solvents (HyperCoal (HPC) production). Changes during solvent extraction depended on the chemical form of nitrogen in the coal. HyperCoal nitrogen primarily consisted of pyrrole nitrogen (pyrrole-N), with less pyridine nitrogen (pyridine-N) and no quaternary nitrogen (quaternary-N). The extracted residue contained pyridine-N and quaternary-N as well as pyrrole-N. Quaternary-N decreased during extraction, while the amount of pyridine-N increased, and relatively a little change was observed in pyrrole-N. It is thought that much of the quaternary-N decomposed during thermal extraction and was converted to pyridine-N. (C) 2012 Elsevier B.V. All rights reserved.