Display omitted ► Studied substitution improved the UV/Fenton degradation of TBBPA on magnetite. ► Some substituting cations can directly produce OH by Fenton-like reaction. ► Cr substituted magnetite is the most promising catalyst for TBBPA degradation. ► Increase in specific surface area and M-OH amount enhanced TBBPA degradation. Magnetite catalysts doped by five common transition metals (Ti, Cr, Mn, Co and Ni) on a similar level were prepared by a precipitation–oxidation method and characterized by chemical analysis, XRD, TG-DSC, BET surface area and XANES. The effects of substituting metal species on the photocatalytic performance of magnetite were investigated and compared through the UV/Fenton degradation of tetrabromobisphenol A (TBBPA). The substitution of above metals improved the heterogeneous UV/Fenton degradation of TBBPA, and the improvement extent increased in the following order: Co<Mn<Ti≈Ni<Cr. Fewer intermediate product species were detected in the systems with higher degradation efficiency. The distinct effects of these substituting metals on the UV/Fenton catalytic activity of magnetite were discussed in terms of reaction mechanism and surface property varieties. The substituting cations participated in the H2O2 decomposition through Haber–Weiss mechanism and enhanced separation and transfer efficiency of the photo-generated electrons and holes, both of which improved the generation of OH free radicals. Furthermore, with larger specific surface area and higher surface hydroxyl amount, substituted magnetite exhibited stronger catalytic activity for TBBPA degradation.