Sulfur adsorption and poisoning of Pt-based catalysts cause an undesired, detrimental effect on performance of proton exchange membrane fuel cells. Here, WO_x is adopted for the first time to modify such noble metal catalysts with an aim of acquiring excellent sulfur tolerance, due to its unique nature with hydrophilicity, redox couple in lower valence, as well as proton spillover effect. A series of WO_x–Pt/C catalysts with various contents of tungsten oxide from 1 to 50 wt% were synthesized and compared to conventional Pt/C catalysts toward sulfur resistance using cyclic voltammetry (CV), as well as rotating ring-disk electrode (RRDE) methods. The results show that the catalyst with 5 wt% WO_x has excellent sulfur tolerance, which might be ascribed to the synergistic effect between WO_x and Pt. The OH groups generated on hydrophilic surfaces of WO_x would accelerate the oxidation of sulfur and lead to rapidly recovering the performance of poisoned WO_x–Pt/C electrodes. The loss of SO_x at the first potential cycling for poisoned WO_x–Pt/C is as high as 51.2% of the total SO_x coverage. Moreover, the higher catalytic activity of WO_x–Pt/C toward oxygen reduction reaction (ORR) is revealed in comparison with Pt/C after both were poisoned by SO_x where the electron transfer number of the former is closer to four-electron than that of the latter. The electronic interaction between Pt and WO_x is evidently confirmed by X-ray photoelectron spectroscopy analysis and strongly suggested as the crucial factor for the ORR enhancement.