A novel homogeneous vanadium-substituted polyoxometalate catalyst of [n-Bu4N](3)H-3[PW9V3O40] showed good catalytic activity for the activation of C-H bonds of toluene and substituted toluene with TBHP (70% aq) under solvent-free conditions. Under the optimal conditions, a 65% yield of benzaldehyde and a TON of 5221 were obtained over this catalyst at 343 K. This catalyst also showed good conversion and selectivity for the oxidation of a series of substituted toluene. The vanadium-substituted Keggin-POM was not decomposed to some species upon the treatment of 530-fold of TBHP by IR characterization. A free radical mechanism was proposed based on the experimental results and the literature supports. (C) 2012 Elsevier B.V. All rights reserved.