Electrochemically driven ion transfer reactions of ClO4-, NO3-, SCN-, and K+ across a cholesterol modified water|nitrobenzene (W|NB) interface have been studied by means of square-wave and cyclic voltammetry at thin organic film modified electrodes. It has been found that cholesterol exhibits a profound accelerating effect toward the kinetics of ClO4-, NO3-, SCN- transfers, whereas a retarding kinetic effect was observed for K+. Besides, the cholesterol layer alters significantly the mechanism of ion transfer, prompting adsorption of all studied ions as a consequence of specific interactions between cholesterol molecules and the transferring ion.