Novel hybrid electrocatalysts were developed based on the attachment of pre-formed capped Pt and PtRu nanoparticles (NPs) on the external surfaces of multi-walled carbon nanotubes (MWCNTs). MWCNTs chemically functionalized by both covalent and non-covalent chemical strategies were tested and evaluated as nanotemplates for the dispersion and stabilization of NPs. The suitable functionalized MWCNTs derivatives were then reacted with pre-formed capped Pt and PtRu NPs yielding the final hybrid materials. The intermediate products as well as the final hybrid materials were characterized in detail with a combination of experimental techniques including Raman spectroscopy, X-ray diffraction, scanning and transmission electron microscopy, while comparative studies regarding their electrocatalytic performance to the oxidation of methanol and ammonia, and to the reduction of hydrogen peroxide were made by performing cyclic voltammetry studies. The results revealed the uniform dispersion of very small NPs along the external surface of functionalized CNTs, while the most suitable electrocatalyst for each particular application is indicated. The chemical strategy followed for the surface functionalization of MWCNTs seems to greatly influence the catalytic activity of the resulting hybrids materials. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.