In the recent years, extensive research work is being carried out and reported on improving the performance of catalysts for both anode and cathode of polymer electrolyte membrane fuel cell (PEMFC). The single cell performance of carbon supported Pt–WO3 electrocatalysts with various compositions (as weight percentage Pt–W 2:8, 4:6, 6:4, 2:8) as anode material was investigated in polymer electrolyte membrane fuel cell and compared to that of 10% Pt/C on the same carbon support and 10% Pt/C (commercial) electrocatalyst. The physical and morphological characterization of the optimized Pt–WO3, 10% Pt/C, 10% Pt/C (commercial) electrocatalysts were further investigated by X-ray diffraction (XRD), cyclic voltammetry, and scanning electron microscopy (SEM) with EDX, transmission electron microscopy (TEM) techniques. The performance of Pt–WO3/C (with a weight percentage of Pt–W 6:4) as anode material was better than those of other compositions of Pt–WO3/C catalyst, 10% Pt/C and 10% Pt/C (commercial). The amount of Pt was also reduced from 1.76 mg cm−2 to 1.046 mg cm−2 which exhibited higher performance in single cell tests.