Abstract A one-dimensional heat transfer method was used to determine the thermal conductivity for a range of coal ash and synthetic ash samples at elevated temperatures. The effect of parameters such as temperature, porosity, and sintering time were investigated. The thermal conductivity of the samples was generally observed to increase with increasing temperature. During heating of the samples, softening of minerals and sintering reactions resulted in changes in the physical structure of the ash, which then altered the observed thermal conductivity. The thermal conductivity of sintered ash samples was found to be higher than that of unsintered samples. The sintering temperature and sintering time were found to increase the observed thermal conductivity irreversibly. A decrease in sample porosity was also observed to increase the thermal conductivity. Chemical composition was found to have little effect on the thermal conductivity, apart from influencing the extent of sintering. Predictions of the thermal conductivity of ash samples based on Rayleigh's model are also presented. The thermal conductivity of slag and particulate structures was modelled by considering spherical pores distributed in a continuous slag phase. A particulate layer structure was modelled by considering solid particles dispersed in a continuous gas phase. The Brailsford and Major model of random distribution for mixed phases gives results within 20% of the measured values for a partially sintered sample.