Rare earth tungsten bronzes, , and those doped with platinum, , were prepared and their electrocatalysis in methanol electro‐oxidation was studied in with at 288–323 K. These electrodes revealed generally a redox behavior due to a couple over 0.15– 0.45V (RHE) and realized after doped with Pt a higher specific electrocatalytic activity than that of ordinary Pt electrodes. Pt electrodes exhibited a low rest potential of 0.30–0.39V (RHE) in the methanol solution and current density of the oxidation of 20–60 μA cm−2 (true) at 0.60V. Also, the heat of activation (10–13 kcal mol−1) was much lower than that on ordinary Pt electrodes (20 kcal mol−1). It was found that the electrocatalytic activity depended upon the lattice constants of bronzes, in a similar manner as the redox potential of couple. Further, the electrodes exhibit a much higher activity towards electro‐oxidation of or of in the presence of as compared with ordinary Pt electrodes. The results suggested a mediatory action of the couple, being effective in oxidative removal of impeding reaction intermediates such as adsorbed .