The compound di-3-n-propyltrimethoxysilane (1,4-diazoniabicycle[2.2.2] octane) dichloride, [(MeO)3Si(CH2)3N +(CH2CH2)3N+(CH 2)3Si(OME)3]Cl2 was obtained and was used as a precursor reagent to obtain hybrid xerogels where the organic molecule was bonded to a silica framework by reacting the ends of both sides of the precursor reagent. That is, both Si(OME)3 groups react with tetraethylorthosilicate (TEOS) by hydrolysis-condensation reactions. The resulting hybrid xerogels with variable C/Si mole ratios were prepared and analyzed and their textural characteristics determined. The samples prepared presented micropores with diameter 1.5 nm, the chain length of which matched with the estimated length of the organic bridging group. The charged organic bridging groups allow the immobilization of hexacyanoferrate ions by an ion exchange process. The electron transfer process of the hexacyanoferrate anionic complex confined in the pores of the matrices was studied by cyclovoltammetry. © 2005 Elsevier Inc. All rights reserved.