Abstract
Molecular dynamics simulations and vibrational sum-frequency spectroscopy are historically the main techniques applied to the description of the molecular structure and dynamics of the immiscible liquid/liquid interface. A molecular sharpness is estimated for oil/water interfaces, with an interfacial width that extends from hundreds of Å to 1 nm. However, electrochemical studies have elucidated a deeper liquid/liquid interface on the order of several micrometers. The breaking down of single-entity electrochemistry to simpler systems and the combination of high-resolution microscopies is confirming a larger extension of the interface. What can be the role of the electrochemist in clarifying this fundamental question? We try to give a suggestion at the end of a brief historical overview of the liquid/liquid interface studies.