The supramolecular association of tetrathiafulvalene (TTF) donors and bipyridinium acceptors is employed routinely to direct the formation of host/guest complexes and interlocked molecules in bulk solution. We have reproduced these donor/acceptor interactions at electrode/solution interfaces and demonstrated their pronounced influence on heterogeneous electron transfer. Specifically, we have synthesized a TTF with an oligomethylene arm terminated by a thiol group and assembled monolayers of this compound on gold. We have observed that the cyclic voltammogram of the immobilized TTF donors varies significantly upon addition of benzyl viologen, tetracyanoquinodimethane (TCNQ), or tetracyanoethylene (TCNE) acceptors to the electrolyte solution. Indeed, the supramolecular association of the complementary donors and acceptors results in a pronounced current decrease for the TTF redox waves. Consistently, the electrochemical response of the acceptors changes dramatically in the presence of TTF donors on the electrode surface. Instead, hexadecanethiolate monolayers, lacking the TTF donors at the termini of the oligomethylene chains, have a marginal influence on the voltammograms of the acceptors. Impedance measurements indicate that the charge-transfer resistance (R-CT) for the reduction of the acceptors increases from less than 0.3 kOmega, at bare gold, to 324, 24, and 43 kOmega for benzyl viologen, TCNQ, and TCNE, respectively, at TTF-coated electrodes. By contrast, the electrode coating has a negligible influence on the cyclic voltammogram and impedance response of ferrocene, which cannot sustain donor/acceptor interactions with the immobilized TTFs. Thus, our results demonstrate that the interfacial complexation of complementary donors and acceptors has a dramatic effect on the heterogeneous electron transfer to and from the associated components.