Ni-Zn and Ni-Zn-P alloys supported on Vulcan XC-72 are effective materials for the spontaneous deposition of palladium through redox transmetalation with PdIVsalts. The materials obtained, Pd-(Ni-Zn)/C and Pd-(Ni-Zn-P)/C, have been characterized by a variety of techniques. The analytical and spectroscopic data show that the surface of Pd-(Ni-Zn)/C and Pd-(Ni-Zn-P)/C contain very small, highly dispersed, and highly crystalline palladium clusters as well as single palladium sites, likely stabilized by interaction with oxygen atoms from NiO moieties. As a reference material, a nanostructured Pd/C material was prepared by reduction of an aqueous solution of PdCl2/HCl with ethylene glycol in the presence of Vulcan XC-72. In Pd/C, the Pd particles are larger, less dispersed, and much less crystalline. Glassy carbon electrodes coated with the Pd-(Ni-Zn)/C and Pd-(Ni-Zn-P)/C materials, containing very low Pd loadings (22–25 μg cm−2), were studied for the oxidation of ethanol in alkaline media in half cells and provided excellent results in terms of both specific current (as high as 3600 A g(Pd)−1at room temperature) and onset potential (as low as −0.6 V vs Ag/AgCl/KClsat).