Pt – Ni nanoparticles were fabricated via the gas phase method. Their performance as anode catalysts for the proton exchange membrane fuel cell was investigated as a function of Ni concentration. The microscopic configurations of the nanoparticles were rather heterogeneous; Pt-rich alloys existed in the core region of particles while a part of the surface layer was composed of the Ni-rich layer. Despite the Ni-rich layer in the shell region, the anode catalyst performance of the Pt – Ni nanoparticles was never deteriorated compared with that of the Pt ones. When the anode catalyst was composed of the Pt nanoparticles, a maximum power density of 112 mW/cm2 was obtained. However, 90% of the power density was still kept even when 40 at. % of Pt was replaced with Ni. The results suggest that a further decrease of Pt composition with maintaining its catalyst performance can be feasible by effective particle dispersing.