A more comprehensive study than those previously reported in the literature was carried out on the electrochemical reduction of 10,10’-dimethyl-9,9’-baicridinium ion (lucigenin) in aqueous solutions. Lucigenin (L(2+)) exhibits one, two, or three irreversible voltammetric reduction peaks, depending on its concentration and the scan rate. The first peak is due to the reduction of the first monolayer of molecules adsorbed on the electrode. This process involves two simultaneous one-electron transfers that yield a molecule (P), also immobilized at the electrode, which undergoes a conformational change to the form P’. In addition, the reagent molecules that reach the electrode by diffusion and the product (P) comproportionate to yield the intermediate radical R(.+). New reactant molecules can displace the product because the monolayer is reversibly adsorbed. The transfer coefficient of the process and the activation energy of the conformational change were determined. The second peak is due to the reduction of a second monolayer of adsorbed lucigenin molecules. This takes place via the first monolayer of product molecules adsorbed on the electrode. Finally, the third peak arises from reduction of lucigenin molecules adsorbed on the previous monolayers. The overvoltage required to reduce lucigenin increases with increasing number of monolayers formed. The formation of new insoluble monolayers blocks the faradaic process altogether in the second scan at more positive potentials than those for the second or third peak.