An electroreflectance method to determine the electron transfer rate constant of a film of redox-active chromophores immobilized on an optically transparent electrode when the surface coverage of the film is very low (<0.1 monolayer) is described herein. The method, potential-modulated total internal reflection fluorescence (PM-TIRF) spectroscopy, is a fluorescence version of potential-modulated attenuated total reflection (PM-ATR) spectroscopy that is applicable when the immobilized chromophores are luminescent. The method was tested using perylene diimide (PDI) molecules functionalized with p-phenylene phosphonic acid (PA) moieties that bind strongly to indium-tin oxide (ITO). Conditions to prepare PDI-phenyl-PA films that exhibit absorbance and fluorescence spectra characteristic of monomeric (i.e., nonaggregated) molecules were identified; the electrochemical surface coverage was approximately 0.03 monolayer. The tilt angle of the long axis of the PDI molecular plane is 58 degrees relative to the ITO surface normal, 25 degrees greater than the tilt angle of aggregated PDI-phenyl-PA films, which have a surface coverage of approximately one monolayer. The more in-plane orientation of monomeric films is likely due to the absence of cofacial pi-pi interactions present in aggregated films and possibly a difference in PA-ITO binding modes. The electron transfer rate constant (k(s,opt)) of monomeric PDI-phenyl-PA films was determined using PM-TIRF and compared with PM-ATR results obtained for aggregated films. For PDI monomers, k(s,opt) = 3.8 x 103 s(-1), which is about 3.7-fold less than k(s,opt) for aggregated films. The slower kinetics are attributed to the absence of electron self-exchange between monomeric PDI molecules. Differences in the electroactivity of the binding sites on the ITO electrode surface also may play a role. This is the first demonstration of PM-TIRF for determining electron transfer rate constants at an electrode/organic film interface.