The facilitated transfer of silver, Ag+, has been studied at the Interface between Two Immiscible Electrolyte Solutions (ITIES). The transfer was achieved with the assistance of a calixarene-based silver ionophore. An investigation of the mechanistic details of the transfer was conducted using cyclic voltammetry at both micro and macro liquid vertical bar liquid interfaces. The mechanism was found to follow a Transfer by Interfacial Complexation (TIC)/Transfer by Organic phase Complexation (TOC) mechanism. The complex stoichiometry was found to shift from 1: 1 to 1:2, metal:ligand, with increasing ionophore concentration. The logarithms of the complex association constants, log beta(1)(0) and log beta(2)(0), were estimated at 12.4 and 14.5, respectively. The charge transfer current was also found to be limited by diffusion of the transferring species and was unchanged by the presence of a range of interferents. The system thus shows promise for selective analytical applications. (c) 2005 Elsevier B.V. All rights reserved.