The use of 2-hydroxybenzophenone (2-HBP) in personal care products is of great concern due to its potential negative effects on the ecosystem and public health. This paper presents the degradation of 2-HBP by bismuth(III) (Bi³⁺)-ferrate(VI) (Fe^VIO₄^2-, Fe(VI)) (Bi³⁺-Fe(VI) system). Experimental studies at different pH and dosages of Bi³⁺ and Fe(VI) showed that the Bi³⁺-Fe(VI) system increased the degradation rate and removal efficiency of 2-HBP compared to Fe(VI) alone. Surface, spectroscopic and electrochemical measurements demonstrated that in situ flake-like white flocculent precipitate of Bi(OH)₃ in the system resulted in enhanced oxidation capacity of Bi³⁺-Fe(VI) system through the valence transition in Bi(III) and Bi(V) to remove 2-HBP. Density functional theoretical (DFT) calculations indicated that the Fe(VI) could oxidize Bi(OH)₃ to form BiO₃^- through a dihydrogen-transfer process. Formation of Bi(V) was also confirmed experimentally and plausible reaction mechanisms of Fe(VI) and Bi(III) were proposed. Seventeen identified transformation products of 2-HBP by Fe(VI) with and without Bi³⁺revealed hydroxylation, bond breaking, carboxylation, and polymerization reaction pathways. Significantly, Bi³⁺ facilitated the polymerization reaction and the dioxygen transfer-mediated hydroxylation reaction pathways. The ions (anions and cations) and humic acids present in the Bi³⁺-Fe(VI) system had minimal influence on the removal efficiency of 2-HBP. Reusability tests and use of real water samples as well as toxicity assessments of transformation products unveiled the practical application aspect of the Bi³⁺-Fe(VI) system. Finally, the results showed that the system exhibits good removal efficiency for all 12 phenolic compounds, indicating the premium universality. The Bi³⁺-Fe(VI) system may be an easy-to-implement cost-effective method for the catalytic degradation of benzophenones by Fe(VI).