The electrochemical behaviors of ten derivatives of ketone as the organic phases for the establishment of liquid/liquid interfaces were investigated by cyclic voltammetry and micropipettes. The ionic species limiting the potential window were determined, and relationships between the structure of solvents and the potential window were evaluated. For heptanones and nonanones, the limits of the potential window were affected by the places of carbonyl and the branched structures in carbon chains. We have found that the water/2,6-dimethyl-4-heptanone interface has the widest potential window among these ten ketone derivatives. Simple ion transfers of TPAs+, TBA(+), BF4-, IO4- and ClO4- were observed at the water/2,6-dimethyl-4-heptanone interface with BTPPATPBCl and LiCl as the respective organic and aqueous supporting electrolytes, and their thermodynamic data were calculated. (C) 2016 Published by Elsevier B.V.