Pt and Pt–Ru shells on Cu cores supported on Vulcan carbon XC72R have been synthesized and tested as possible anode electrocatalysts for polymer electrolyte fuel cells. Pt(Cu)/C was prepared by Cu electrodeposition on the black carbon support at constant potential followed by Pt deposition on Cu by galvanic exchange, whereas Pt–Ru(Cu)/C was prepared by spontaneous deposition of Ru species on Pt(Cu)/C. The corresponding cyclic voltammograms in 0.5 M H2SO4 solution showed the hydrogen adsorption/desorption peaks and no Cu oxidation. The respective CO stripping peak potentials of Pt(Cu)/C and Pt–Ru(Cu)/C were about 0.1 and 0.2 V more negative than those corresponding to Pt/C and Ru-decorated Pt/C. The best conditions for CO oxidation were found for Cu deposition potentials between −0.2 and −0.4 V vs. Ag/AgCl/KCl(sat). The Pt economy of the Pt–Ru(Cu)/C system was proved for the methanol oxidation, with specific currents more than twice those obtained on the Ru-decorated commercial Pt/C catalysts.