The kinetics of proton transfer facilitated by 4-octylaniline, 4-dodecylaniline and 4-hexadecylaniline across the water/1,2-dichloroethane interface has been investigated by cyclic voltammetry and ac impedance. It was found that their electrochemical behaviour is very similar and the three amines assist proton transfer from the aqueous to the organic phase. The formal Gibbs energy of proton transfer and the formal rate constant were evaluated. It is concluded that interfacial organisation of these molecules is an important factor in the kinetics of facilitated proton transfer and that the aromatic ring is able to penetrate the interface whilst the long hydrophobic chain contributes to the stability of the amine in the organic phase. (C) 2004 Elsevier Ltd. All rights reserved.