Photodecomposition of bromophenols

•Photodecomposition serves as a potent elimination corridor for BPs in the environment.•PBs decompose more effectively in the gaseous phase than in the aqueous phase.•Photoreactivity of BPs decreases along the following sequence ortho > meta > para.•TDDFT calculations reveal that higher brominated congeners display lower excitations energies, and are more labile to photodebrominate.