Brominated aromatic rings constitute main structural entities in virtually all commercially deployed brominated flame retardants (BFRs). Oxidative decomposition of BFRs liberates appreciable quantities of bromobenzenes (BBzs). This contribution reports experimental measurements for the generation of notorious polybrominated dibenzofurans (PBDFs) and polybrominated diphenyl ethers (PBDEs) from oxidation of monobromobenzene (MBBz). In the light of developed product profiles, we map out reaction pathways and report kinetic parameters for PBDFs and PBDEs formation from coupling reactions of MBBz molecule and its derived ortho-bromophenoxy (o-BPhxy) radical using quantum chemical calculations. The identification and quantitation of product species involve the use of gas chromatograph - triple quadrupole mass spectrometer (GC-QQQMS) operating in the multiple reaction monitoring (MRM) mode. Bimolecular reactions of MBBz and o-BPhxy result in the generation of twelve pre-PBDF intermediates, of which four can also serve as building blocks for the synthesis of PBDEs. These four intermediates are denoted as pre-PBDE/pre-PBDF, with the remaining eight symbolised as pre-PBDF. The resonance-stabilised structure of the o-BPhxy radical accumulates more spin density character on its phenoxy O atom (30.9 %) in reference to ortho-C and para-C sites. Thus, the formation of the pre-PBDE/pre-PBDF structures via O/o-C couplings advances faster as it requires lower activation enthalpies (79.2 – 84.9 kJ mol−1) than the pre-PBDF moieties, which arise via pairing reactions involving o-C(H or Br)/o-C(H or Br) sites (97.2 – 180.2 kJ mol−1). Kinetic analysis indicates that, the O/o-C pre-PBDE/pre-PBDF adducts self-eject the out-of-plane H atoms to produce PBDEs, rather than undergo a three-step mechanism forming PBDFs. However, experimental measurements demonstrate PBDEs appearing in lower yields as compared to those of PBDFs; presumably due to H- and Br-induced conversion of the PBDEs into PBDFs following a simple ring-closure reaction. High reaction temperatures facilitate loss of ortho Br atom from PBDEs, followed by cyclisation step to generate PBDFs. PBDFs are observed in a narrow temperature range of 700–850 °C, whereas PBDEs form between 550–850 °C. Since formation mechanisms of PBDFs and polybrominated dibenzo-p-dioxins (PBDDs) are typically only sensitive to the bromination at ortho positions, the results reported herein apply also to higher brominated isomers of BBzs.