In this work, we experimentally revealed the thermochemical decomposition pathway of Decabromodiphenyl ethane (DBDPE) and tetrabromobisphenol A (TBBPA) containing electronic waste plastics using an online thermogravimetric-fourier transform infrared-mass spectroscopy (TG-FTIR-MS) system, a high resolution gas chromatography/high resolution mass (HRGC-MS) spectroscopy, and a fixed-bed reactor. We found the distribution and species of produced bromides can be easily controlled by adjusting pyrolytic temperature, which is particularly crucial to their recycle. From the analysis of the liquid and solid phase obtained from the fixed-bed reactor, we proposed that the Br-center dot radicals formed during the pyrolysis process may be captured by organic species derived from the depolymerization of plastics to form brominated compounds or by the inorganic species in the plastics, and that these species remained in the char residue after pyrolysis. Our work for the first time demonstrates intramolecular oxygen atoms play a pivotal role in the formation of PBDD/Fs that pyrolysis of oxygen-free BFRs is PBDD/Fs-free, whereas pyrolysis of oxygen-containing BFRs is PBDD/Fs-reduced. (C) 2016 Elsevier B.V. All rights reserved.