A series of composite solid superacid catalysts SO 4 2− /ZrO 2 -M x O y (M=Ti, Ni, Si) were prepared and investigated by means of Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). All catalysts exhibit good catalytic activity in the electrochemical reaction of p-xylene with methanol assisted with a pair of porous graphite plane electrodes and the selectivity of main products higher than 90% were observed. In particular, SO 4 2− /ZrO 2 -SiO 2 catalyst exhibited excellent catalytic activity. According to the experimental results, a possible free radical reaction mechanism confirmed by XPS and ultraviolet–visible (UV–vis) spectra was proposed. It may be concluded that a simple and feasible electrochemical catalytic oxidation reaction at room temperature and standard atmosphere may be possible.