We prepared ferrocene-modified silicon surfaces through a three-step procedure consisting of the photochemical anchoring of 11-bromo-1-undecene on H-Si(I 00), followed by treatment with NaN3 and by a reaction with ethynylferrocene via azide-alkyne Huisgen cycloaddition reaction, also known as "click" chemistry. The advantages of this approach are multiple: the synthetic approach is flexible, provided a C C tethering arm is present on the molecule of interest; a self-assembled hydrocarbon chain can guarantee a good coverage and resistance to the further synthetic steps; the redox centers are located at the outer surface, where a good contact with the electrolyte becomes possible. We have monitored the progression of the reaction steps by XPS, and characterized the resulting new hybrid on Si by electrochemical methods. The presence and chemical nature of the redox species covalently attached to the SAM on Si has been evaluated by XPS, while the overall coverage has been calculated by CV measurements. A reversible electrochemical response has been evidenced for the hybrids and the progressive ageing followed at thousands of oxidation-reduction cycles. (c) 2007 Elsevier Ltd. All rights reserved.