A set of NaCl-loaded coal samples was prepared by physically impregnating NaCl into a Victorian (Loy Yang) brown coal. This set of brown coal samples was pyrolysed in a thermogravimetric analyser and in a novel fluidised-bed/fixed-bed reactor. The latter reactor has some features of both a fluidised-bed reactor and a fixed-bed reactor. The reactor configuration allowed the volatilised Na to be swept away by carrier gas from the bed of char particles, avoiding the re-condensation of the volatilised Na on the char particles at lower temperatures. The volatilisation of Na and of Cl during pyrolysis was quantified simultaneously. The results indicated that a significant proportion of Cl could be volatilised at temperatures around 200 degreesC. The volatilisation of Cl increased drastically with increasing temperature, from 200 to about 500 degreesC. At higher temperatures with a fast heating rate, Cl could interact with the nascent char to be retained in the char. The volatilisation of Na followed a different trend from that of Cl and increased monotonically with increasing temperature. The loading of NaCl into the brown coal had negligible effects on the total volatile yields and on the volatilisation of Mg and Ca during pyrolysis. It is concluded that NaCl in the brown coal was mainly released as Na and Cl separately rather than as NaCl molecules. Reactions involving radicals play important roles in the volatilisation of Na and Cl.