Electrochemical studies of new binary Pt-MoC electrocatalysts prepared by carbothermal-reduction method have been developed. The XRD and XPS characterization allows to determine the structure of core-shell Mo-carb-particles, with a reduced-Mo core (Mo2C, MoO2 and/or Mo-0) and a MoO3-shell (2-3 nm). Upon adding Pt, Pt interacts with MoO3-shell. The oxidation of: (i), CO by cyclic voltamperometry (CV) followed by in situ differential electrochemical mass spectrometry (DEMS); and, (ii), methanol by CV and chronoamperometric techniques were carried out at room temperature. The results show an improvement in the Pt-tolerance to CO-presence with the presence of reduced Mo-carb phases (decreasing the potential in 65 mV(RHE)), without significant difference between the binary catalysts. An additional Mo-redox pre-peak is observed at 0.4(RHE) V. This process is related to Mo4+-to-Mo6+ oxidation developed on the MoO3-shell of Mo-carb-particles, which is catalysed by Pt. This Mo-oxidation/reduction couple is affected (shifts towards more negative potentials) by the CO adsorption on Pt-centres. DEMS results show that CO-oxidation occurs in the potential region of this Mo-oxidation. The binary Pt-Mo-carb catalysts show similar behaviour for methanol oxidation as those for CO-stripping ones. Nevertheless, the chronoamperometric curves display a catalytic performance improvement (highest activity and stability) using Pt-MoC/CBv catalyst regarding the other binary catalysts. This best behaviour with Mo2C-phase enhances to increases the temperature up to 60 degrees C (typical value for low-temperature FCs in-operation). Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.