This study focused on the investigation of the thermal degradation process of tetrabromobisphenol A (TBBA). The use of combined experimental techniques allowed the quantitative characterization of TBBA decomposition products and the analysis of the thermal degradation rates. The distribution of bromine among the different decomposition product fractions was investigated. In the open configuration used for the experiments, hydrogen bromide, brominated bisphenol A species, and brominated phenols resulted in the main decomposition products. Bromine was mainly evolved as hydrogen bromide, although a relevant quantity resulted present in the primary high molecular weight condensable product fraction, in agreement with the decomposition pathways proposed. The results evidenced that accidents involving TBBA thermal degradation, such as fire or process runaways, may pose relevant safety problems because of the possible release of considerable quantities of hazardous decomposition products.