The area of fire protection has grown over the last decades with an increasing use of brominated flame retardants (BFRs). Some of the BFRs are phenolic compounds as applied, e.g. tetrabromobisphenol A and 2,4,6-tribromophenol. Others, like the polybrominated diphenyl ethers (PBDEs), can be metabolized to phenolic compounds, i.e. polybrominated phenoxyphenols (OH-PBDEs). OH-PBDEs, have to our knowledge never been commercially produced, but some are well known natural products, and found in high concentrations in biota. The present study is aimed to determine the susceptibility of OH-PBDEs to undergo photolysis when dissolved in water and to compare their reactivity with a couple of PBDE congeners. A previously developed method for studies of photolysis was applied and adapted to include OH-PBDEs in water at pH 7 and 11, water/methanol and water/hydrogen peroxide. The results indicate a change in reaction rates for the photolysis of OH-PBDE in different aqueous media and pH dependence. The results from the present study show that hydroxylated compounds rapidly undergo photolytic transformations in water. The OH-PBDEs are more rapidly transformed then PBDE congeners with similar numbers of bromine substituents. All the OH-PBDEs, independent of structure, are rapidly transformed, with approx. the same rate, when hydrogen peroxide is present, indicating another route of reaction. Polybrominated dibenzo-p-dioxins (PBDDs) are indicated as transformation products upon photolysis of OH-PBDEs with a favorable bromine substitution pattern.