Brominated polycyclic aromatic hydrocarbons (BrPAHs) have been consistently detected in various environmental matrices, and measured at alarming rates in stack emissions. However, formation mechanisms and bromination patterns of BrPAHs remain unclear. This contribution constructs detailed mechanistic pathways for the synthesis of selected BrPAHs (namely bromine-bearing naphthalene, acenaphthylene, anthracene, and phenanthrene). Mapped-out pathways follow the Bittner-Howard's route in the hydrogen abstraction acetylene addition (HACA) mechanism, in which a second C2HBr molecule is added to the first one. Constructed kinetic model portrays temperature-dependent profiles of major and minor species. Direct loss of an H atom from the acetylenic fragment appears to be more important at elevated temperatures, when compared with further addition of C2HBr cuts or ring-cyclization reactions. The occurrence of closed-shell Diels-Alder pathway should be inhibited owing to sizable enthalpic barriers. Fukui Indices for electrophilic substitutions (f-1) establish bromination' s pattern of selected BrPAHs. The diradical character of BrPAHs coupled with electron-deficient C(Br) sites, render BrPAHs as potent precursors for the formation of environmentally persistent free radicals (EPFRs). Findings reported herein shall be useful in comprehending the formation chemistry of BrPAHs, a less-investigated category of toxicants in thermal systems.