In order to obtain uniform and reproducible surface enhanced Raman spectroscopy (SERS) platforms, a novel method for deposition of well adhered multifarious gold particles on a tin doped indium oxide electrode through electrogeneration at an electrode gold compound, in toluenelaqueous-electrolyte three-phase junction was developed. The electrodeposition was carried out both by double-potential-step chronoamperometry with one pulse for nucleation and I one for growth of the particles, and by potentiostatic single-potential-step chronoamperometry. Both procedures give angular, multifarious Au particles with a diameter of 150 +/- 40 nm. The size of the particles is independent of deposition time, after an initial growth phase, and controlled by the formation of a microemulsion at the three-phase junction. The particles are likely deposited from the microdioplets and their size is determined by the amount of gold salt in a droplet The mechanism involves electoreduction of tetraoctylammonium tetrachloroaurate at the tin doped indium oxide electrode followed by ion transfer across the liquidlliquid interface. The Au particles are strongly adhered to the electrode surface. the Au particle covered electrode enhances Raman scattering on the order of 10(5)-10(5) times for malachite green isothiocyanate. Surface enhanced Raman spectroscopy studies reveal that the reproducibility of the Au particle deposit is excellent both between samples (<15% RSD) and across a single sample (<12% RSD). The obtained nanoparticulate deposit was also demonstrated to show electrocatalytic activity toward dioxygen reduction.