The rate of electron self-exchange reactions between discretely charged metal-like cores of nanoparticles has been measured in multilayer films of nanoparticles by an electrochemical method. The nanoparticles an Au monolayer-protected clusters with mixed monolayers of hexanethiolate and mercaptoun-decanoic acid ligands, linked to each other and to the Au electrode surface with carboxylate-metal ion-carboxylate bridges. Cyclic voltammetry of the nanoparticle films exhibits a series of well-defined peaks for the sequential, single-electron, double-layer charging of the 1.6-nm-diameter Au cores. The electron self-exchange is measured as a diffusion-like electron-hopping process, much as in previous studies of redox polymer films on electrodes. The average electron diffusion coefficient is D-E = 10(+/-5) X 10(-8) cm(2)/S, With no discernible dependence on the state of charge of the nanoparticles or on whether the reaction increases or decreases the core charge. This diffusion constant corresponds to an average first-order rate constant k(HOP) of 2(+/-1) X 10(6) s(-1) and an average self-exchange rate constant, k(EX), of 2(+/-1) x 10(8) M-1 s(-1), using a cubic lattice hopping model. This is a very large rate constant, considering the nominally lengthy linking bridge between the Au cores.