AbstractIn this study, Fe3O4@TiO2 was synthesized by a facile precipitation–impregnation method and applied as a magnetic photocatalyst for degrading synthetic and actual textile dyeing wastewater in the presence of peroxymonosulfate (PMS). In Rhodamine B (RhB) degradation, the removal efficiency reached 99.86% (for RhB) and 93.67% (for color) under optimal operating conditions of 80 mg L–1 RhB, 0.5 g L–1 PMS, 0.5 g L–1 Fe3O4@TiO2, at pH 6, and after 30 min of UVA irradiation. The influence levels of anions on the RhB removal and decolorization were in the order of Cl− < SO42− < CO32− < PO43−. In addition, the Fe3O4@TiO2 composite exhibited good applicability for treating other dyes (e.g., 99.6% of tartrazine and 60.3% of methylene blue after 30 min) in water and actual textile dyeing wastewater with high color (70.3% after 5 min) and COD removal (71.4% after 120 min). The radical scavenging tests indicated the role of reactive oxygen species in the order of O2•− ∼ 1O2 > h+ > SO4•− > HO• for RhB degradation but O2•− > h+ > 1O2 > SO4•− > HO• for decolorization. These results suggest the potential application of PMS activation using Fe3O4@TiO2 in the photocatalytic treatment of textile and dyeing wastewater with the dominant role of O2•−.