The electrocatalyst PtBi with a Pt solid-solution phase has been synthesized using sodium hypophosphite as a reducing agent. The results of X-ray diffraction and X-ray absorption near-edge spectroscopy showed that in the presence of P, the Pt-Bi system forms an alloy with a Pt face-centered cubic solid-solution phase structure. Electrochemical test results revealed that PtBi/XC-72 exhibited a good electrocatalytic activity in the oxidation of methanol.