The deposition mechanism of metallic gold was investigated based on charge transfer voltammetry at the water/1,2-dichloroethane (W/DCE) interface, and the corresponding redox voltammetry of the metal precursor in W and the reductant, triphenylamine (TPA), in DCE. The metal precursor was present as Au(III) (AuCl4-), or Au(I) (AuCl2-) in W or DCE. Electron transfer could be observed voltammetrically at the interface between W containing both Au precursors and DCE containing TPA. Au particles, formed by constant potential electrolysis at the W/DCE interface, were examined by transmission electron microscopy. It was shown that deposit size could be controlled via the applied potential and time, with specific conditions to form particles of less than 10 nm identified. (C) 2014 The Authors. Published by Elsevier Ltd. All rights reserved.