The electrochemical behavior of ferrocene moieties immobilized by covalent grafting on ordered mesoporous silica samples has been studied by cyclic voltammetry in aqueous medium using carbon paste electrodes modified with these solids. The functionalized silica samples were obtained using (3-(ferrocenylamide)propyl)triethoxysilane as the grafting agent. The results have been discussed in relation to the ferrocene content in the materials and compared to those obtained with non-ordered ferrocene-grafted silica gels. Well-defined voltammetric signals have been observed in spite of the insulating character of the mesoporous silica matrix and they were found to increase as a function of the ferrocene groups content in the material. They displayed a better stability upon continuous cycling potentials in comparison to those recorded with amorphous gels, suggesting a beneficial effect of the long-range structural order on the electron transfer processes in such confined media. (c) 2006 Elsevier Ltd. All rights reserved.