Most of the electrochemical reactions involved in fuel cell are structure sensitive. Moreover, for the electrooxidation of small organic molecules catalysts have to be multifunctional. For these reasons, the development Of various synthesis methods of multimetallic electrocatalysts allowing to control the atomic composition and the microstructure is needed in order to improve the electrocalalytic activity. For this purpose, several methods for the preparation of nanostructured catalysts have been developed in our laboratory (impregnation-reduction method. colloidal route. carbonyl route, microemulsion and electrochemical methods), which allow to prepare multimetallic particles. These catalysts were characterized using physical and physico-chemical methods (XRD, TEM, EDX, electrochemical methods, etc.) in order to check their composition, structure, dispersion. active surface area, etc. Amongst the developed methods, some of them can lead to the formation of alloyed or non-alloyed multimetallic compounds depending on the synthesis procedure. XRD analysis allows us to discriminate the catalyst structures. The influence of the atomic composition and of the nature of foreign metals added to platinum is discussed in terms of electrochemical activity towards oxidation of small organic molecules of interest in energy storage and production. In particular, it appears that non-alloyed Pt-Ru catalysts display higher electroactivity towards methanol oxidation. Electrochemical and DEMS measurements were used to study and to evaluate the influence of the electrocatalyst structure on its electroactivity. The effect of the composition in terms of foreign metal atoms and atomic content of platinum based and platinum-tin based catalysts towards the electrooxidation of ethanol is also discussed from electrochemical experiments and fuel cell test results. (c) 2007 Elsevier Ltd. All rights reserved.