A ferric smectite clay material was synthesized and further intercalated with Al2O3 pillars for the first time with the aim of evaluating its ability to be used as heterogeneous catalyst for the photo-Fenton decolorization of azo dye Orange II. UV irradiation was found to enhance the activity of the catalyst in the heterogeneous photo-Fenton process. Catalyst loading of 0.5 g/L and hydrogen peroxide concentration of 13.5 mM yielded a remarkable color removal, accompanied by excellent catalyst stability. The decolorization of Orange II followed the pseudo-first-order kinetics for initial dye concentrations from 20 to 160 mg/L. The central composite design (CCD) based on the response surface methodology (RSM) was applied to evaluate the effects of several operating parameters, namely initial pH, catalyst loading and hydrogen peroxide concentration, on the decolorization efficiency. The RSM model was derived and the response surface plots were developed based on the results. Moreover, the main intermediate products were separated and identified using gas chromatography-mass spectrometry (GC-MS) and a possible degradation pathway was proposed accordingly. The acute toxicity experiments illustrated that the Daphnia magna immobilization rate continuously decreased during 150 min reaction, indicating that the effluent was suitable for sequential biological treatment. (C) 2015 Elsevier B.V. All rights reserved.