The gross chemical structures of xylites and gelified soft brown coal woods, Latrobe Valley, Victoria, Australia, as determined by solid state nuclear magnetic resonance spectroscopy, are compared with those of present-day wood-derived materials prepared from an angiosperm, Eucalyptus regnans, and a gymnosperm (conifer), Pinus radiata. Also examined are the changes in the gross chemical structures of soft brown coal woods with increase in their degree of gelification and the relationship between these changes and variations in their chemical composition and microscopic appearance. The Victorian xylites exhibit greater affinities with the present-day gymnosperm than the present-day angiosperm. The progressive removal of cellulose with increasing degree of gelification can be equated with an increase in huminite reflectance, elimination of humotelinite autofluorescence and changes in the relative proportions of the humotelinite submacerals. The lignin structure of xylite is also modified during the gelification process, including the progressive loss of methoxyl groups and evidence of minor oxidation.