Methoxymethyl benzene was synthesized through direct oxidation of toluene in methanol at room temperature and standard atmosphere using an electrochemical catalytic reactor assisted by SO42-/Fe2O3-MoO3 catalyst has been studied by UV-vis spectrum and gas chromatography/mass spectrometry (GC/MS). This new system showed a high selectivity to methoxymethyl benzene, minimizing its over-oxidation and other by-products production. SO42-/Fe2O3-MoO3 catalysts were prepared and characterized by Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). The effect of various dosage of MoO3 in the catalyst was also investigated. The results showed that 5.0 g SO42-/Fe2O3-20% MoO3 as the catalyst, 3.0 g KF as the assisted catalyst, current intensity at 0.8 A for 120 min at room temperature (298 K), gave the better system performance in terms of produced methoxymethyl benzene with high selectivity (51.341%). (C) 2008 Elsevier B.V. All rights reserved.