In order to protect human health and the environment, several regulations have been introduced in recent years to reduce or even eliminate the use of some brominated flame retardants (BFRs) due to their toxicity, persistence and bioaccumulation. Dispersions of these BFRs in polymers are widely used for various applications. In this report, four different brominated molecules, decabromodiphenyl ether (DBDE), hexabromocyclododecane (HBCDD), decabromodiphenyl ethane (DBDPE) and tris(tribromophenoxy)triazine (TTBPT), were dispersed in the solid matrix of an industrial polymer, high impact polystyrene (HIPS). The possibility of degradation of these BFRs within HIPS under UV–visible irradiation in ambient air was investigated. The degradation kinetics of DBDE and HBCDD were followed by Fourier transform infrared spectroscopy (FTIR) and high-resolution two-step laser mass spectrometry (L2MS). The thermal properties of the pristine and irradiated polymer matrix were monitored by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), which showed that these properties were globally preserved. Volatile photoproducts from the degradation of DBDE, DBDPE and TTBPT were identified by headspace gas chromatography/mass spectrometry analysis. Under the chosen experimental conditions, BFRs underwent rapid degradation after a few seconds of irradiation, with conversions exceeding 50% for HIPS/DBDE and HIPS/HBCDD systems.