Evidence for the competition between long-range electron transfer across self-assembled monolayers (SAMs) and incorporation of the redox probe into the film is reported for the electroreduction of Ru(NH3)(6)(3+) at hydroxyl- and carboxylic-acid-terminated SAMs on a mercury electrode, by using electrochemical techniques that operate at distinct time scales. Two limiting voltammetric behaviors are observed, consistent with a diffusion control of the redox process at mercaptophenol-coated electrodes and a kinetically controlled electron transfer reaction in the presence of neutral HS-(CH2)(10)-COOH and HS-(CH2)(n)-CH2OH (n = 3, 5, and 10) SAMs. The monolayer thickness dependence of the standard heterogeneous electron transfer rate constant shows that the electron transfer plane for the reduction of Ru(NH3)(6)(3+) at hydroxyl-terminated SAMs is located outside the film I solution interface at short times. However, long time scale experiments provide evidence for the occurrence of potential-induced gating of the adsorbed structure in some of the monolayers studied, which takes the form of a chronoamperometric spike. Redox probe permeation is shown to be a kinetically slow process, whose activation strongly depends on redox probe concentration, applied potential, and chemical composition of the intervening medium. The obtained results reveal that self-assembled monolayers made of mercaptobutanol and mercaptophenol preserve their electronic barrier properties up to the reductive desorption potential of a fully grown SAM, whereas those of mercaptohexanol, mercaptoundecanol, and mercaptoundecanoic acid undergo an order/disorder transition below a critical potential, which facilitates the approach of the redox probe toward the electrode surface.