Interfacial charge-transfer rate constants have been measured for n-type Si electrodes in contact with a series of viologen-based redox couples in methanol through analyses of the behavior of these junctions with respect to their current density versus potential and differential capacitance versus potential properties. The data allow evaluation of the maximum rate constant (and therefore the electronic coupling) for majority carriers in the solid as well as of the dependence of the rate constant on the driving force for transfer of delocalized electrons from the n-Si semiconducting electrode into the localized molecular redox species in the solution phase. The data are in good agreement with existing models of this interfacial electron transfer process and provide insight into the fundamental kinetic events underlying the use of semiconducting photoelectrodes in applications such as solar energy conversion.