AuNi alloy was synthesized by vacuum arc melting in high-purity argon atmosphere. The AuNi alloy was characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). The results of EDS indicated that Au and Ni atoms were well-distributed in the alloy. Moreover, the results of XPS exhibited an electronic transfer from Ni to Au in AuNi phase. The Electrocatalytic oxygen reduction reaction (ORR) activity and the methanol tolerance of the AuNi alloy were respectively investigated using the RDE method and the electrochemical cyclic voltammetry. The results suggested that O2 was directly oxidized to H2O on the AuNi catalyst via an approximate four-electron reduction pathway, and that the AuNi catalyst had a high electrocatalytic activity for the ORR and an acceptable methanol tolerance, simultaneously.