A heteropolyanion-based cross-linked ionic copolymer was prepared by the anion-exchange of heteropolyacid (HPA) H5PMo10V2O40 with polymeric ionic liquid (PIL) poly(divinylbenzene-3-n-butyl-1-vinylimidazolium)Br, and characterized by FI-IR, UV-vis, XRD, TG, SEM, elemental analysis and BET surface areas. The characterization results show that the ionic copolymer is an amorphous HPA salt of PIL-cation with a considerable thermal stability, high surface area and large pore volume. Further, the ionic copolymer is revealed to be a highly efficient heterogeneous catalyst for hydroxylation of benzene with H2O2 to phenol, showing high activity, convenient recovery and steady reuse. The excellent performance of the novel porous HPA-based copolymer catalyst is discussed in relation to its textural property and intramolecular charge transfer behavior. (C) 2012 Elsevier B.V. All rights reserved.