Composite electrodes were prepared from chemical vapor deposition grown carbon nanofibers consisting predominantly of ca. 100 nm diameter fibers. A hydrophobic sol-gel matrix based on a methyl-trimethoxysilane precursor was employed and composites formed with carbon nanofiber or carbon nanofiber-carbon particle mixtures (carbon ceramic electrode). Scanning electron microscopy images and electrochemical measurements show that the composite materials exhibit high surface area with some degree of electrolyte solution penetration into the electrode. These electrodes were modified with redox probe solution in 2-nitrophenyloctylether. A second type of composite electrode was prepared by simple pasting of carbon nanofibers and the same solution (carbon paste electrode). For both types of electrodes it is shown that high surface area carbon nanofibers dominate the electrode process and enhance voltammetric currents for the transfer of anions at liquid vertical bar liquid phase boundaries presumably by extending the triple-phase boundary. Both anion insertion and cation expulsion processes were observed driven by the electro-oxidation of decamethylferrocene within the organic phase. A stronger current response is observed for the more hydrophobic anions like ClO4- or PF6- when compared to that for the more hydrophilic anions like F- and SO42-.