Iron tetrapolyvanadate (Fe2V4O13) was prepared and characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) measurement and scanning electron microscopy (SEM). It was found that Fe2V4O13 could effectively catalyse H2O2 to generate active OH; therefore, Fe2V4O13 was employed as a new two-metal heterogeneous Fenton-like catalyst. The decomposition of H2O2 and the degradation of Acid Orange II catalysed by Fe2V4O13 could be well described with a simple pseudo-first-order rate equation between the reaction temperatures of 15 degrees C and 30 degreesC. It was inferred from the reaction activation energy data that the generation of the hydroxyl radical was a control step in a series of reactions for the oxidation of Acid Orange II in the presence of H2O2 and Fe2V4O13. The catalytic activity of Fe2V4O13 towards degradation of Acid Orange II was not only much higher than that of alpha-Fe2O3, V2O5 and FeVO4 but also than that of their mixtures with an identical ratio of Fe and V, such as 2FeVO4 + V2O5 and Fe2O3 + 2V2O5. The high catalytic activity possibly involved a special two-way Fenton-like mechanism and the synergistic activation of Fe(III) and V(V) in Fe2V4O13 towards H2O2.