A successful approach to prepare the Pd–Ni nanowire arrays electrode without carbon supports was reported. The morphology and crystallinity of nanowire were characterized by transmission electron microscopy, selected-area electron diffraction(SAED), X-ray diffraction(XRD), and X-ray photoelectron spectroscopy(XPS) analyses, respectively. The results show that the diameters of the nanowire are in the range of 65–75 nm, and the polycrystalline binary solid solution alloy is formed in the Pd–Ni nanowire. Cyclic voltammograms, chronoamperograms, and electrochemical impedance spectroscopy demonstrate that the Pd–Ni nanowire arrays electrodes show excellent electrocatalytic performance for methanol oxidation in alkaline media. The catalytic activity of Pd–Ni nanowire arrays electrode is *1.39 times higher than that of the Pd nanowire arrays electrode and *2.28 times higher than that of the commercial Pd/C catalyst. This is mostly owing to the transfer of electron density from Ni to Pd. These results indicate that Pd–Ni nanowire arrays electrode is very promising in an alkaline direct methanol fuel cell.
