Four carbon supported PtCu nanostructured catalysts with Pt:Cu atomic ratios of 1:3.20, 1:2.23, 1:0.61 and 1:0.35 were synthesized by a two-step route, involving the chemical reduction of Cu ions on the carbon support, followed by the partial galvanic replacement of Cu atoms by Pt. Bimetallic nanostructured particles with average sizes in the range of 2.3 3.2 nm were obtained. The bimetallic catalysts with surface Pt contents between 20 and 55 at. % were formed by a Cu-rich core surrounded by a Pt-Cu shell, while that with the highest Pt content presented a uniform alloy structure instead of a core-shell arrangement. The electrocatalytic performance of the as-prepared materials toward ethanol electrooxidation in acid and alkaline media and glycerol oxidation in alkaline environment was investigated by cyclic voltammetry and chronoamperometry. It was observed that the electrocatalytic activity of PtCu nanoparticles was found to depend on the surface composition, platinum utilization efficiency, structure and Pt ensemble. Among the as prepared catalysts, Pt0.62Cu0.38/C core-shell material showed the best performance for ethanol oxidation in both acid and alkaline environments, while Pt0.24Cu0.7/C and Pt0.31Cu0.69/C core-shell catalysts exhibited the highest activity for glycerol oxidation in alkaline medium. The electrochemical results showed that the catalytic activity of the bimetallic Cu@PtCu core-shell nanostructured nanoparticles is between four and ten times higher than that of a commercial Pt0.51Ru0.49/C catalyst. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.