The kinetics of transport phenomena generated by an electric field and leading to the formation of density gradients in suspensions of charged colloidal silica were studied by using various electrodes. The rate of approach to a steady-state density gradient was found to be much higher when using metallic electrodes (Cu, Fe, and Pt) in comparison with graphite (C) electrodes. Nevertheless, the initial rate with C electrodes was substantially increased by the addition of hydroquinone-quinone because the redox reactions, necessary for electrode-electrolyte current transfer, occur at lower potential compared with the electrolysis of water. On the other hand, the products of oxidation of hydroquinone which accumulate in the system bring about an important decrease of the zeta potential of silica particles and progressive deceleration of their electrophoretic mobility. A detailed study was carried out, by using thin-layer isoperichoric focusing, UV-vis spectrophotometry, and voltamperometry, to explain the observed phenomena which can interfere in electric polarization or focusing field-flow fractionation.