Decades after phasing out their production and use, especially in the formulations of brominated flame retardants (BFRs), polybrominated biphenyls (PBBs) still pose serious environmental and health problems. The oxidation of PBB has been hypothesised as a pathway for the formation of the notorious polybrominated dibenzofurans (PBDFs) and their dispersion in the environment. However, the exact reaction corridor remains misunderstood, with the existing mechanisms predicting the reaction to proceed via a high energy process that involves the breakage of C-C linkage (~118.0kcalmol-1) and the subsequent formation of bromophenols molecules, where the latter are supposed to act as precursors for the formation of PBDFs (~40.0-60.0kcalmol-1). Herein, we show that PBBs produce PBDFs in a facile mechanism through a series of highly exothermic reactions (i.e., overall barriers reside 8.2-10.0kcalmol-1 below the entrance channel). Whilst the fate of the ROO-type intermediates in oxidation of all aromatics is to emit CO or CO2, PBDFs constitute the dominant products from the oxidation of PBBs. Initially formed R-OO adduct evolves in a very exoergic mechanism to yield PBDFs. In view of the facile oxidative transformation of PBBs into PBDFs, we conclude that, it is unsafe to dispose BFRs in oxidation processes, as this practice generates high yields of toxic PBDFs.