It is established experimentally using H-1 NMR wide line spectroscopy that methane can exist in coals not only in open or closed porosity and fracture systems but also in solid solutions in coal substance, in particular, under methane pressure 2 MPa or higher. Methane dissolved in coal minerals reversibly modifies their lattice parameters as determined from X-ray diffraction analysis. Co-existence of these methane forms in fossil coals causes multi-step desorption kinetics. It is shown experimentally that the long-term latent methane desorption is effected mainly by closed porosity. which in turn is determined by coal rank. (C) 2004 Published by Elsevier Ltd.