The accurate determination of the thermal properties of biomass materials is particularly important when studying biomass combustion processes. This paper reports a method for the determination of the maximum sampling error and the confidence intervals of thermal properties obtained from TG-DSC analysis. Special care must be taken with the sampling procedure to achieve an acceptable degree of error and low statistical uncertainty. The obtained levels of uncertainty and error demonstrate that the properties evaluated by the analysis were representative of the fuels. A study of the trends and time correlations was performed to ensure that the observed correlations arise from completely random causes. The obtained results are particularly interesting for biomass energy applications. (C) 2012 Elsevier Ltd. All rights reserved.