We propose a detailed study of the interfacial structuring of a non-halogenated, and tribologically relevant, ionic liquid (IL) at an electrified interface, as a function of applied potential, its concentration (in a base fluid) and exposure to water (via addition of small water concentrations). We have already performed nano- and macro-scale tribological measurements on IL mixtures, which show clear changes in friction coefficient with applied potential and water exposure. Therefore, we expect to observe considerable changes in the IL boundary layers. Through integration with our ongoing tribology tests, we hope our results will help guide the application of ILs as future electro-responsive ‘tribotronic’ lubricants or lubricant additives, as well as provide a launch pad for other electrochemical applications where responsive interfacial structures are likely to play a key role.