We have previously observed that primary coal extracts recovered from the flowing solvent reactor appeared to be of large molecular mass. Short residence times in the reaction zone following the solubilisation of the extracts tended to limit their thermal degradation. This observation offered the vista of detailed characterisation and analysis of most (similar to 80-90%) of the coal mass in solution-and in a state relatively free of thermal degradation. Point of Ayr coal was extracted with tetralin and with non-donor solvents, quinoline and NMP at 350 and 450 degreesC. Structural evaluations have been carried out using size exclusion chromatography, UV-fluorescence spectrometry, GC-MS and probe-MS. Little coal derived material could be found in the pentane-soluble part of the reaction mixture; solvent dimers and trimers were prominent and coal-derived components, such as alkanes, were only minor components. In attempting to characterise the main, pentane-insoluble fraction of the coal extract, the level of interference from solvent-derived material emerged as the decisive parameter for the success or failure of the general method. However, the predominantly pentane-insoluble coal extracts from each solvent were contaminated by solvent polymerisation products. For all three solvents, the level of contamination of extracts with solvent derived material tended to interfere with the detailed characterisation/analysis of material extracted from the coal. (C) 2004 Elsevier Ltd. All rights reserved.