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.