The electrochemical catalytic reaction of toluene with methanol, assisted with a pair of porous graphite plate electrodes, catalyzed by solid superacid of cobalt modification catalyst with chemical conversion higher than 81%, was described and investigated by UV-vis spectrum, scan electron microscopy (SEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and gas chromatography-mass spectrometry (GC-MS). A possible free radical reaction mechanism was proposed. It may be concluded that a simply and feasible electrochemical catalytic coupling oxidation reaction at room temperature and air pressure may be possible. (C) 2007 Elsevier B.V. All rights reserved.