It was reported for the first time that phosphorictungstenic acid (PWA) could promote the oxygen reduction reaction (ORR) and inhibit the methanol oxidation reaction at the cathodic Pt/C catalyst in the direct methanol fuel cell (DMFC). When the weight ratio of PWA to Pt/C is 1, the composite catalyst increases the reduction current of oxygen by about 38% and decreases the oxidation current of methanol by about 76% compared with that of the Pt/C catalyst.