Mesoporous silica thin films were shown to be an appropriate matrix for immobilization of discrete electroactive moieties, yielding uniform transparent thin film electrodes with defined texture and enhanced electrochemical activity. The mesoporous silica films prepared on conducting FTO-coated glass substrate were postsynthetically functionalized. Alkoxysilanes were used as precursors for subsequent grafting via ionic or covalent bonds of representative electroactive species, such as polyoxometalate PMo12O403-, hexacyanoferrate(III), and ferrocene. The electrochemically active concentration within the silica-based composite electrodes achieves 90, 260, and 60 mu mol cm(-3) for polyoxometalate, hexacyanoferrate(III), and ferrocene, respectively. The amount of molecules involved in the charge-transfer sequence is proportional to the film thickness and comparable to the total amount of embedded guests. Thus, eventually the whole bulk volume of the modified silica films is electrochemically accessible. Immobilization in the chemically modified silica matrix alters the redox potential of the electroactive molecules. Electron exchange between the adjacent redox centers (electron hopping) is proposed as a possible charge propagation pathway through the insulating silica matrix, which is supported by the fact that the high charge uptake is observed also for the hybrid electrodes with the covalently anchored redox guests.