A series of novel catalysts that P, Mo metal-salt (MxOy-MoO3-P2O5, M = Fe, Ni, Cu) were prepared and investigated by means of TGA-DSC, XRD and XPS for elemental mapping. All catalysts exhibited good catalytic activity in the reaction of toluene with methanol, assisted with a pair of porous graphite plane electrodes, and chemical conversion higher than 92% was observed. In particular, iron promoted catalysts exhibited excellent catalytic activity. According to the experimental results, a possible free-radicals reaction mechanism confirmed by XPS and UV-vis spectra was proposed. (C) 2007 Elsevier B.V. All rights reserved.