The assisted transfer of silver ion, Ag+, by complexation of Ag+ with the tetrakis(4-chlorophenyl)borate (TPBCl-) anion was studied at the interface between two immiscible electrolyte solutions (ITIES).The elucidation of the interfacial mechanisms employed the cyclic voltammetry technique applied to macro and micro liquid/liquid interfaces. This procedure allowed to identify Ag+ as the species which is transferred at the liquid/liquid interface and also the formation of an 1:2 metal:ligand complex when TPBCl- is in excess.The value for the formal transfer potential of silver(I) from aqueous to 1,2-dichloroethane was evaluated and the association constant for the [Ag(TPBCl)(2)](-) complex was determined. (C) 2003 Elsevier Ltd. All rights reserved.