Hydroxylated polyhalodiphenyl ethers (HO-PXDEs) have attracted considerable scientific interest as examples of emerging aquatic pollutants. However, a comprehensive assessment of disposal methods for this particular pollutant was seldom investigated. This study examined the UV light degradation of HO-PXDEs, using 2'-HO-2, 3', 4, 5'-tetrabromodiphenyl ether (2'-HO-BDE-68) as a case study. The results showed that UV light was superior to visible light and electron beam irradiation for producing a high degradation rate of 2'-HO-BDE-68. At low concentrations of HO-BDE, the degradation rate was not obviously improved with decreasing initial concentration. The degradation efficiency was also found to be better in alkaline solutions. In a UV/H2O2 system, the hydroxyl radical provided by H2O2 was shown to enhance the degradation efficiency. The main photolysis products of 2'-HO-BDE-68 were identified, and the possible photodegradation pathways were proposed. 1, 3, 8-Tribromodibenzo-p-dioxin was one of the photoproducts, which indicates that secondary pollution must also be considered with the UV photolysis process.