A new heterogeneous Fenton-like system, consisting of V-MCM-41 catalyst and hydrogen peroxide, was proved to be effective in removing recalcitrant dye Rhodamine B (RhB) in aqueous solutions. V-MCM-41 was prepared following a direct hydrothermal procedure with tetraethyl silicate and ammonium metavanadate as precursor. The mesoporous structure has been characterized by XRD, and the specific surface area was determined as x m2 g−1 according to BET method. The catalytic reaction can proceed in a relatively wide pH range from acidic to alkaline. And the visible light irradiation cannot promote the reaction process. In addition, the mechanism implication for V-MCM-41 as a Fenton-like catalyst has been discussed.