A series of SO42-/MxOy (M = Fe, Zr, Sri, Ti, and Sb) catalysts were prepared and investigated by means of Fourier transform infrared (FTIR), powder X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Its application in the synthesis of methoxymethyl benzene from the electrochemical reaction of toluene with methanol assisted by a pair of porous graphite plane electrodes with selectivity higher than 75% was also studied. According to the experimental results, a possible radical cation 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. In comparison to methyl tert-butyl ether (MTBE), methoxymethyl benzene used as a booster to improve fuel combustion was also studied.