Hydroxylated polybromodiphenyl ethers (OH-PBDEs) are emerging aquatic pollutants, but their origins in the environment are not fully understood. There is evidence that OH-PBDEs are formed from bromophenols, but the underlying transformation processes remain unknown. Here, we investigate if the photoformation of OH-PBDEs from 2,6-dibromophenol in aqueous solution involves 2,6-bromophenoxyl radicals. After the UV irradiation of an aqueous 2,6-dibromophenol solution, HPLC-LTQ-Orbitrap MS and GC-MS analysis revealed the formation of a OH-PBDE and a dihydroxylated polybrominated biphenyl (di-OH-PBB). Both dimeric photoproducts were tentatively identified as 4'-OH-BDE73 and 4,4'-di-OH-PBB80. In addition, three debromination products (4-OH-BDE34, 4'-OH-BDE27, and 4,4'-di-OH-PBBs) were observed. Electron paramagnetic resonance spectroscopy revealed the presence of a 2,6-dibromophenoxyl radical with a six-line spectrum (a(H) (2 meta) = 3.45 G, a(H) (1 para) = 1.04 G, g = 2.0046) during irradiation of a 2,6-dibromophenol solution in water. The 2,6-dibromophenoxyl radical had a relatively long half-life (122 ± 5 μs) according to laser flash photolysis experiments. The para-para C-C and O-para-C couplings of these 2,6-dibromophenoxyl radicals are consistent with the observed formation of both dimeric OH-PBDE and di-OH-PBB photoproducts. These findings show that bromophenoxyl radical-mediated phototransformation of bromophenols is a source of OH-PBDEs and di-OH-PBBs in aqueous environments that requires further attention.