Fenton and photoassisted Fenton degradation of ordinary hydrophobic cross-linked polystyrene microspheres and sulfonated polystyrene beads (DOWEX 50WX8) have been attempted. While the Fenton process was not able to degrade these polystyrene materials, photoassisted Fenton reaction (mediated by broad-band UV irradiation from a 250 W Hg(Xe) light source) was found to be efficient in mineralizing cross-linked sulfonated polystyrene materials. The optimal loadings of the Fe(III) catalyst and the H(2)O(2) oxidant for such a photoassisted Fenton degradation were found to be 42 μmol-Fe(III) and 14.1 mmol-H(2)O(2) per gram of the sulfonated polystyrene material. The initial pH for the degradation was set at pH 2.0. This photoassisted Fenton degradation process was also able to mineralize commonly encountered polystyrene wastes. After a simple sulfonation pretreatment, a mineralization efficiency of >99% (by net polymer weight) was achieved within 250 min. The mechanism of this advanced oxidative degradation process was investigated. Sulfonate groups introduced to the surface of the treated polystyrene polymer chains were capable of rapidly binding the cationic Fe(III) catalyst, probably via a cation-exchange mechanism. Such a sorption of the photoassisted Fenton catalyst was crucial to the heterogeneous degradation process.