In this paper, we describe a novel method for measuring the forward heterogeneous electron-transfer rate constant (kf) through the thiol monolayer of gold monolayer protected clusters (MPCs) in solution using scanning electrochemical microscopy (SECM). Applying the equations for mixed mass-transfer and electron-transfer processes, we develop a new formula using only the diffusion coefficient and the tip radius and use it as part of a new method for evaluating SECM approach curves. This method is applied to determine the electron-transfer rates from a series of SECM approach curves for monodisperse hexanethiol MPCs and for polydisperse hexanethiol, octanethiol, decanethiol, dodecanethiol, and 2-phenyethylthiol gold MPCs. Our results show that as the alkanethiol length increases the rate of electron transfer decreases in a manner consistent with the previously proposed tunneling mechanism for the electron transfer in MPCs. However, the effective tunneling coefficient, Beta, is found to be only 0.41 A-1 for alkanethiol passivated MPCs compared to typical values of 1.1 A-1 for alkanethiols as self-assembled monolayers on two-dimensional gold substrates. Similar SECM approach curve results for Pt and Au MPCs indicate that the electron-transfer rate is dependent mostly on the composition of the thiol layer and not on differences in the core metal.