Voltammetry with arrays of immobilised (redox active) oil droplets on graphite electrodes immersed in aqueous solution has proven to be a viable method to study ion transfer at the liquid-liquid interface. In this paper, we report on the inverse experiment, where water droplets are immobilised on a graphite electrode and then immersed into 1,2-dichloroethane containing tetrabutylammonium perchlorate as the supporting electrolyte. The voltantmetry of water droplets containing both supported and unsupported redox systems is studied. In addition, electro deposition experiments provide unarguable evidence for the heterogeneous reaction at the 3 phase boundary. (c) 2005 Elsevier B.V. All rights reserved.