Decabromodiphenylether (DBDE) is a brominated flame retardant which belongs to the group of polybromodiphenylethers (PBDEs) often used as a fire resistant additive in various well known polymeric systems like polystyrene, poly(acrylonitrile-butadiene-styrene) (ABS), polypropylene, etc. This compound can be considered as a persistent organic pollutant and presents certain risks for the environment owing to the fact that it is bioaccumulable and not biodegradable. A detailed investigation, described here, was carried out on the effect of ultraviolet/visible radiation on DBDE in ABS with the aim to study the photolytic reactions of this molecule in the solid state, in order to improve the economic and ecological treatment of brominated plastic waste from waste electrical and electronic equipment (WEEE). This study presents new aspects of the photochemical degradation of DBDE/ABS systems in the solid state. The photodegradation of DBDE in ABS was followed by Fourier transform infrared spectroscopy (FTIR) as well as by thermogravimetrical analysis (TGA). Good agreement was obtained for the results of both analytical methods in terms of the overall photolysis of DBDE.