A new amino-functionalized bipyridine-heteropolyacid ionic hybrid was prepared by protonating and anion-exchanging the amino-attached bipyridine ionic liquid with phosphotungstic acid, and characterized by FT-IR, H-1 NMR, UV-vis, XRD, SEM, TG, BET surface area, melting point, and elemental analysis. Its catalytic activity was evaluated in the oxidation of benzyl alcohol with aqueous H2O2. The hybrid catalyst is proved to be a highly efficient solid catalyst for solvent-free oxidation of benzyl alcohol with H2O2, which is featured by the fast reaction rate, high conversion and selectivity, easy recovery, and quite steady reuse. (C) 2012 Elsevier B.V. All rights reserved.