The work presented herein deals with the study of the influence of the synthesis conditions on the properties of carbon xerogels (CXGs). The study analyzes the effect of the composition of the mixture of carbon gel precursors and the pH on the porous structure, the arrangement of carbon, the surface chemistry and the electrical conductivity. Certain conditions allow obtaining CXGs with a high porosity, high ordering and polymerization degree. CXGs are used as Pt catalyst supports for the electro-oxidation of methanol. CXGs with the higher ordering and polymerization degree result in catalysts with low crystal sizes and good metallic distribution. Such catalysts show the highest activities towards methanol oxidation. CXG-supported Pt catalysts outperform a Vulcan-supported Pt catalyst prepared in the same conditions. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.