A novel experimental methodology for depositing and voltammetric study of Ag nanoparticles at the water nitrobenzene (W-NB) interface is proposed by means of thin-film electrodes. The electrode assembly consists of a graphite electrode modified with a thin NB film containing decamethylferrocene (DMFC) as a redox probe. In contact with an aqueous electrolyte containing Ag+ ions, a heterogeneous electron-transfer reaction between DMFC(NB) and Ag-(w)(+) takes place to form DMFC(NB)+ and Ag deposit at the W-NB interface. Based on this interfacial reaction, two different deposition strategies have been applied. In the uncontrolled potential deposition protocol, the electrode is immersed into an AgNO3 aqueous solution for a certain period under open circuit conditions. Following the deposition step, the Ag-modified thin-film electrode is transferred into an aqueous electrolyte free of Ag+ ions and voltammetrically inspected. In the second protocol the deposition was carried out under controlled potential conditions, i.e., in an aqueous electrolyte solution containing Ag+ ions by permanent cycling of the electrode potential. In this procedure, DMFC(NB) is electrochemically regenerated at the electrode surface, hence enabling continuation and voltammetric control of the Ag deposition. Hence, the overall electrochemical process can be regarded as an electrochemical reduction of Ag-(w)(+) at the W-NB interface, where the redox couple DMFC+/DMFC acts as a mediator for shuttling electrons from the electrode to the W-NB interface. Ag-particles deposited at the W-NB interface affect the ion transfer across the interface, which provides the basis for voltammetric inspection of the metal deposit at the liquid-liquid interface with thin-film electrodes. Voltammetric properties of thin-film electrodes are particularly sensitive to the deposition procedure, reflecting differences in the properties of the Ag deposit. Moreover, this methodology is particularly suited to inspect catalytic activities of metal particles deposited at the liquid-liquid interface toward heterogeneous electron-transfer reactions occur-ring at the at the liquid-liquid interface.