Electrocatalysts with constant metallic composition, consisting of carbon-supported platinum and molybdenum phases, were synthesized following the thermolysis (thr) and borohydride (bhr) reduction methods and using different metallic precursors. The obtained electrocatalysts were characterized by X-ray energy-dispersive spectrometry, X-ray diffraction and high resolution transmission electron microscopy. Their activities were studied by cyclic voltammetry. Different surface structures were obtained and the electrochemical activities toward methanol oxidation were compared. Pt, MoO2 and MoO3 phases were well identified with the characterization techniques used. However, the electrochemical responses obtained from both sample series were considerably different, suggesting that the arrangement and relationships between active phases strongly depend on the synthesis method and aggregation sequence of the metallic precursors, and being the cause of different catalytic activities and stabilities of molybdenum oxide phases. The bhr method offered higher activity than the thr method. Among the sample series obtained by bhr method, the catalyst obtained by platinum deposition on the previously synthesized molybdenum on carbon, led to the highest overall activity. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: [email protected]. All rights reserved.