The catalytic efficiency of iron (II, III) oxide to promote Fenton-like reaction was examined by employing Rhodamine B (RhB) as a model compound at neutral pH. Two types of iron (II, III) oxides were used as heterogeneous catalysts and characterized by XRD, Mossbauer spectroscopy, BET surface area, particle size and chemical analyses. The adsorption to the catalyst changed significantly with the pH value and the sorption isotherm was fitted using the Langmuir model for both solids. Both sorption and FTIR results indicated that surface complexation reaction may take place in the system. The variation of oxidation efficiency against H2O2 dosage and amount of exposed surface area per unit volume was evaluated and correlated with the adsorption behavior in the absence of oxidant. The occurrence of optimum amount of H2O2 or of exposed surface area for the effective degradation of RhB could be explained by the scavenging effect of hydroxyl radical by H2O2 or by iron oxide surface. Sorption and decolourization rate of RhB as well as H2O2 decomposition rate were found to be dependent on the surface characteristics of iron oxide. The kinetic oxidation experiments showed that structural Fell content strongly affects the reactivity towards H2O2 decomposition and therefore RhB decolourization. The site density and sorption ability of RhB on surface may also influence the oxidation performance in iron oxide/H2O2 system. The iron (II, III) oxide catalysts exhibited low iron leaching, good structural stability and no loss of performance in second reaction cycle. The sorption on the surface of iron oxide with catalytic oxidation using hydrogen peroxide would be an effective oxidation process for the contaminants. (C) 2008 Elsevier B.V. All rights reserved.