In this paper, CuO and CeO2 were screened as co-catalyst components for Fe2O3/attapulgite (ATP) catalyst, and three new catalysts (CuO-Fe2O3/ATP, CeO2-Fe2O3/ATP and CuO-CeO2-Fe2O3/ATP) were prepared for degradation of methylene blue (MB). The three catalysts' characteristics were determined by BET, XRD, FT-IR, SEM and XPS. MB degradation in different systems and at different pH values was also studied. Under the conditions of H2O2 concentration of 4.9 mmol L-1, catalyst dosage of 5 g L-1, pH of 5, reaction temperature of 60 °C and MB initial concentration of 100 mg L-1, the as-synthesized catalysts showed much greater reaction rate and degradation efficiency of MB than Fe2O3/ATP catalyst. In addition, the reusability of the as-prepared composites was evaluated. The intermediate products of MB degradation were identified by LC-MS and the possible degradation process of MB was put forward. This journal is © The Royal Society of Chemistry.