This work analyses a set of perhydrous coals (mainly composed of huminite/vitrinite maceral group) in order to determine the inter-relations between the hydrogen content and the modifications in the coal structure at a molecular level. The study involves the direct solid state characterisation of the coal combined with the analysis of representative fragments of the coal network obtained through flash-pyrolysis. The perhydrous character of the coals is not reflected either in the aliphatic hydrogen concentration (from FTIR data) or by the presence of straight-chain aliphatic moieties in the pyrolysates. This structural study shows that perhydrous coals contain mainly aromatic structures with 1–2 rings and a very small concentration of aromatic rings of large size. In agreement with this, phenol and alkyl phenols are the most prominent degradation products whereas other aromatic compounds (mainly benzene and naphthalene derivatives) are minor and probably evaporative compounds. The major structural elements in the samples studied are simple phenols with a preponderance of substituted para alkyl. The results obtained show that the processes of hydrogen enrichment affect the reactions of aromatisation and condensation. During the natural evolution of the perhydrous coals the transformations of the oxygenated functionalities in the lignin precursor seem to have taken place without the parallel structural reorganisation of the lignin framework responsible for the formation of polycyclic aromatic systems. As a result, the chemical structure of perhydrous vitrinites in coals is substantially modified with respect to that described in ‘normal' coals. The results obtained also indicate that the source of hydrogen content and the effect that it has during the subsequent evolution process of the coals, affects the chemical structure of the perhydrous vitrinite and hence its properties and behaviour.Financial support for this work was provided through a contract with the European Community (No. 7220/EC-769).Peer reviewed