Carbon nanotubes (CNTs) supported palladium–iron bimetallic nanoparticles (Pd–Fe/CNTs) catalyst is synthesized using palladium hexacyanoferrate (PdHCF) as reaction precursor. In this method, the negatively charged PdHCF nanoparticles self-assemble on the positively charged polydiallyldimethylammonium chloride (PDDA) functionalized CNTs through electrostatic interaction, and then are reduced to Pd–Fe alloy nanoparticles by sodium borohydride. The physicochemical properties of Pd–Fe/CNTs are investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). These structural analyses reveal that the Pd–Fe/CNTs catalyst possesses the high alloying degree and the small particle size. Electrochemical measurements show that the eletrocatalytic activity of the Pd–Fe/MWCNTs catalyst for the methanol oxidation is better than that of the Pd/CNTs catalyst, which originates from the synergistic effect between Pd atom and Fe atom.