The growing world population is contributing to the increasing amounts of waste and a significant increase in energy demand. Therefore, coal will increasingly be replaced by refuse-derived fuel (RDF), which is produced from municipal solid waste. The use of such fuel poses many difficulties because of its heterogeneity and high mercury emission. One method to stabilize the properties of RDF and reduce the mercury content is thermal pretreatment. The purpose of this study was to investigate the release of mercury from RDF samples following thermal pretreatment. The study was carried out in the temperature range of 100−350 °C. Statistical analysis was performed on the correlation between the composition of the RDF samples and the release of mercury. The RDF samples showed a very high variation in the mercury content, ranging from 45 to 849 µg Hg/kg (1.7 to 35.3 µg Hg/MJ). Thermal pretreatment removed a significant amount of mercury at 250 °C (94−99%). Paper content positively affected mercury release. Relatively low correlation coefficients were obtained in the statistical analysis, which may be explained by the significant heterogeneity of the RDF samples magnified by the variability in the mercury content within particular fractions.