Brominated flame retardants (BFRs) are bromine-bearing hydrocarbons added or applied to materials to increase their fire resistance. As thermal treatment and recycling are common disposal methods for BFR-laden objects, it is essential to precisely describe their decomposition chemistry at elevated temperatures pertinent to their thermal recycling. Laboratory-level and pilot-scale investigations have addressed the thermal decomposition of pure BFRs and/or BFR-laden polymers under oxidative and pyrolytic environments, typically at temperatures of 280–900 °C. These studies shed light on the effects of various factors influencing the decomposition behaviour of BFRs such as chemical character, polymer matrix, residence time, bromine input, oxygen concentration, and temperature. Although BFRs decomposition mainly occurs in a condensed phase, gas phase reactions also contribute significantly to the overall decomposition of BFRs. Exposing BFRs to temperatures higher than their melting points results in evaporation. Quantum chemical calculations have served to provide mechanistic and kinetic insights into the chemical phenomena operating in decomposition of BFRs and subsequent emissions of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs). Under thermal conditions such as smouldering, municipal waste incineration, pyrolysis, thermal recycling, uncontrolled burning and fires, BFRs degrade and form brominated products of incomplete combustion (BPICs). Thermal degradation of BFRs often proceeds in the presence of bromine atoms which inhibit complete combustion. Major BPICs comprise brominated benzenes and phenols in addition to a wide range of brominated aromatics. Pyrolytic versus oxidative conditions seems to have very little influence on the thermal stability and decomposition behaviour of commonly-deployed BFRs. Thermal degradation of BFRs produces potent precursors to PBDD/Fs. Experimental studies have established inventories of PBDD/F emissions with alarming high yields for many BFRs. Co-combustion of BFRs-containing objects with a chlorine source (e.g. polyvinyl chlorides) results in the emission of significant concentrations of mixed halogenated dibenzo-p-dioxins and dibenzofurans (i.e. PXDD/Fs). Formation of PBDD/Fs from incomplete BFRs decomposition occurs primarily due to the condensations of gas phase precursors, including unaltered structural entities of some BFRs in their own right. Complete destruction of BFRs promotes PBDD/Fs formation via de novo synthesis. Bromination of PBDD/Fs in gas phase reactions is more prevalent if compared with chlorination mechanisms of PCDD/Fs, which is largely dominated by heterogeneous pathways. In uncontrolled burning and in simulated fly ash experiments, a strong correlation between congeners patterns of polybrominated diphenyl ethers (PBDEs) and PBDD/Fs indicate that PBDEs function as direct precursors for PBDD/Fs, even in the de novo synthesis route. In this review, we critically discuss current literature on BFRs thermal decomposition mechanisms; gather information regarding the contribution of homogenous and heterogeneous routes to overall BFRs decomposition; survey all studies pertinent to the emission of PBDD/Fs and their analogous mixed halogenated counterparts from open burning of e-waste, and finally, highlight knowledge gaps and potential directions that warrant further investigations.