This study demonstrates the electrochemical conversion of the synthetic procedure of monolayer-protected clusters using a thin toluene layer over an edge plane pyrolytic graphite electrode. A thin toluene layer with a thickness of 0.31 mm was coated over the electrode and an immiscible liquid/liquid water/toluene interface was introduced. The transfer of the tetrachloroaurate ($AuCl_4^-$) ions into the toluene layer interposed between the aqueous solution and the electrode surface was electrochemically monitored. The $AuCl_4^-$ ions initially could not move through into the toluene layer, showing no reduction wave, but, in the presence of the phase transfer reagent, tetraoctylammonium bromide (TOABr), a cathodic wave at 0.23 V vs. Ag/AgCl was observed, indicating the reduction of the transferred $AuCl_4^-$ ions in the toluene layer. In the presence of dodecanethiol together with TOABr, a self-assembled monolayer was formed over the electro-deposited metallic gold surface. The E-SEM image of the surface indicates the formation of a highly porous metallic gold surface, rather than individual nanoparticles, over the EPG electrode.