A wire-mesh reactor capable of multi-step heating/holding and minimising secondary reactions of volatiles was used to investigate the effects of thermal pretreatment in inert gas on the subsequent rapid pyrolysis behaviour of Loy Yang brown coal. Our results indicate that the presence of small amounts (< 10 wt%) of moisture in brown coal has little influence on the tar and char yields from the pyrolysis of brown coal at 1000 K s(-1). While the hydrogen bonds between the moisture and the O-containing functional groups in the brown coal have little effects on its pyrolysis behaviour, the hydrogen bonds among the O-containing functional groups tend to induce cross-linking reactions to reduce the tar yields. Preheating the brown coal at > 250 degrees C leads to reduced tar and increased char yields. However, the characterisation of tars using UV-fluorescence spectroscopy indicates that significant decreases in the release of larger aromatic ring systems are only observed after preheating at > 380 degrees C for 30 min. The presence of ion-exchangeable cations (e.g. Ca2+) in the brown coal tends to stabilise the carboxylate groups and only preheating at > 350 degrees C would result in changes in pyrolysis yields during the subsequent pyrolysis at 1000 K s(-1). These results may be explained by considering the formation of cross-links involving peripheral groups at low preheating temperatures and the formation of cross-links involving aromatic ring systems at elevated temperatures. (c) 2005 Elsevier Ltd. All rights reserved.