Carbon (50-150 nm diameter) nanofibers were embedded into easy to prepare thin films of a hydrophobic sol-gel material and cast onto tin-doped indium oxide substrate electrodes. They promote electron transport and allow efficient electrochemical reactions at solid/liquid and at liquid/liquid interfaces. In order to prevent aggregation of carbon nanofibers silica nanoparticles of 7 nm diameter were added into the sol-gel mixture as a "surfactant" and homogeneous high surface area films were obtained. Scanning electron microscopy reveals the presence of carbon nanofibers at the electrode surface. The results of voltammetric experiments performed in redox probe-ferrocenedimethanol solution in aqueous electrolyte solution indicate that in the absence of organic phase, incomplete wetting within the hydrophobic film of carbon nanofibers can cause hemispherical diffusion regime typical for ultramicroelectrode like behaviour. The hydrophobic film electrode was modified with two types of redox liquids: pure tert-butylferrocene or dissolved in 2-nitrophenyloctylether as a water-insoluble solvent and immersed in aqueous electrolyte solution. With a nanomole deposit of pure redox liquid, stable voltammetric responses are obtained. The presence of carbon nanofibers embedded in the mesoporous matrix substantially increases the efficiency of the electrode process and stability under voltammetric conditions. Also well-defined response for diluted redox liquids is obtained. From measurements in a range of different aqueous electrolyte media a gradual transition from anion transfer dominated to cation transfer dominated processes is inferred depending on the hydrophilicity of the transferring anion or cation. (c) 2006 Elsevier Ltd. All rights reserved.