Pt(Cu)/C and Pt-Ru(Cu)/C electrocatalysts with core-shell structure supported on Vulcan Carbon XC72R have been synthesized by potentiostatic deposition of Cu nanoparticles on the support, galvanic exchange with Pt and spontaneous deposition of Ru species. The duration of the electrodeposition time of the different species has been modified and the obtained electrocatalysts have been characterized using electrochemical and structural techniques. The High Resolution Transmission Electron Microscopy (HRTEM), Fast Fourier Transform (FFT) and Energy Dispersive X-ray (EDX) microanalyses allowed the determining of the effects of the electrodeposition time on the nanoparticle size and composition. The best conditions identified from Cyclic Voltammetry (CV) corresponded to onset potentials for CO and methanol oxidation on Pt-Ru(Cu)/C of 0.41 and 0.32 V vs. the Reversible Hydrogen Electrode (RHE), respectively, which were smaller by about 0.05 V than those determined for Ru-decorated commercial Pt/C. The CO oxidation peak potentials were about 0.1 V smaller when compared to commercial Pt/C and Pt-Ru/C. The positive effect of Cu was related to its electronic effect on the Pt shells and also to the generation of new active sites for CO oxidation. The synthesis conditions to obtain the best performance for CO and methanol oxidation on the core-shell Pt-Ru(Cu)/C electrocatalysts were identified. When compared to previous results in literature for methanol, ethanol and formic acid oxidation on Pt(Cu)/C catalysts, the present results suggest an additional positive effect of the deposited Ru species due to the introduction of the bifunctional mechanism for CO oxidation.