The hybrid catalysts, pyridine (Py) modified molybdovanadophosphates with Keggin Structure Py-n-PMo(12-m)VmO40 (n = 1-3, m = 1-3), were prepared and characterized by FF-IR. Among various catalysts, Py-1-PMo10V2O40 exhibited the highest yield of phenol (20.5%) with the selectivity of phenol of 98.0% at 353 K for 5 h in the direct hydroxylation of benzene to phenol with H2O2 in the acetic acid and acetonitrile (volume ratio 1:1) mixed solvent. Pyridine plays an important role in the promotion of the catalytic activities, mostly clue to the electronic interaction between pyridine and heteropolyacid together with the more remarkable pseudo-liquid-phase behavior The influences of the reaction temperature. the amount of H2O2, the amount of Py-1-PMo10V2O40 and the reaction tinge on the yield of phenol were investigated to obtain the optimal reaction conditions for phenol formation. (C) 2008 Elsevier B.V. All rights reserved.