The aqueous self-assembly of methyl-terminated tri(oxyethylene)thiol-encapsulated gold nanoclusters of varying core size is demonstrated on micrometer scale Au/SiO2 interdigital electrodes. This self-assembly process consists of alternate exposures of the substrate to solutions of either an alpha,omega-dithiol or the gold nanoclusters, resulting in the deposition of these materials onto the electrode surface. A comparison of the procedure in both H2O and CHCl3 solvents shows that the assembly, as monitored by the electrical conductivity of the device, occurs more rapidly in the H2O system. This observation is complimented by XPS and UV/Vis measurements, which show that (1) the increased current is due to an increased amount of gold deposited on the surface under aqueous conditions and (2) the thiol exchange reaction occurs more rapidly in H2O in comparison to CHCl3.