We have compared the elimination of 5-bromosalicylic acid (BSA) in the systems of goethite (α-FeOOH)/H₂O₂ and lepidocrocite (γ-FeOOH)/H₂O₂. The results demonstrated that BSA (10 mg L⁻¹) could be successfully adsorbed on α- and γ-FeOOH (0.5 g L⁻¹) and then effectively degraded after the addition of H₂O₂ (14.7 mM). BSA adsorption on both α- and γ-FeOOH followed pseudo-second order adsorption kinetic models, with γ-FeOOH having greater adsorption ability than α-FeOOH. In the α-FeOOH/H₂O₂ system, BSA degradation was well fitted with the pseudo-second order kinetics, whereas the oxidation in γ-FeOOH/H₂O₂ system had a two-stage pseudo-first order kinetics. Electron paramagnetic resonance (EPR) results for these two systems revealed the presence of •OH and •OOH, and further tests with radical captures demonstrated their dominance in degrading BSA. Based on the electronic structure analysis, electrons were more easily transferred from the H₂O₂ molecule to the Fe atoms of α-FeOOH, explaining the density functional theory (DFT) calculation results, which showed that α-FeOOH performed better in catalyzing the decomposition of H₂O₂. However, the free radicals are more likely to desorb from γ-FeOOH, which made the γ-FeOOH/H₂O₂ system more efficient in degrading BSA.