FT-IR/Raman spectroscopies have been used to identify the structural features of Victorian brown coal chars during the gasification in air at 400 degrees C. The deconvolution of the Raman spectra has allowed us to identify the main structural sites in char where preferential reaction with O-2 takes place. The presence of Na and Ca catalysts is shown to alter the reaction pathways between char and O-2. In the absence of a catalyst, the O-containing functional groups formed in char during gasification were closely associated with the aromatic structure and thus tended to loosen the aromatic structure. The non-catalysed gasification was slow and took place on some specific (especially sp(3)-rich or sp(2)-sp(3) mixture) sites distributed throughout the char. In the presence of a catalyst (Na or Ca), the O-containing functional groups were not closely associated with the main aromatic structure throughout the char. The catalytic gasification reactions were localised on the sites associated with the catalysts. The preferential removal of smaller aromatic ring systems and the persistence of cross-linking structures in the presence of a catalyst mean that the large aromatic ring systems were increasingly concentrated with little flexibility, affecting the dispersion of catalyst. (C) 2006 Elsevier Ltd. All rights reserved.