The transfer of Cs+ across the water \ 1,2-dichloroethane interface assisted by dibenzo-18-crown-6 (DB 18C6) was studied using cyclic voltammetry in a concentration range aide enough to fulfil the following experimental conditions: c(Cs)(w) >> c(DB18C6)(o), cCs(w) congruent to c(DB18C6)(o) and cCs(w) << c(DB18C6)(o). In all cases, the total voltammetric current comprises two transfer processes which were compared with the theoretical voltammograms for facilitated transfer by using different models. From the results obtained, a first electrochemical step of Cs' transfer with interfacial formation of the complex (Cs: DB18C6) 1:2 was followed by a second electrochemical step with formation of the complex 1:1. The relative contribution of each process to the global current depends on the concentration ratio (lambda = c(Cs)/c(DB18C6)) employed. At high lambda values, the 1:1 complex is formed through the interfacial destruction of the 1: 2 complex and at low lambda values, through the facilitated transfer of M(w) by L(o). An important aspect which results from the treatment carried out is that not only the ratio but also the concentration values determine the appearance of one or two processes. Spectroscopic UV-visible experiments corroborate this postulate.