Interfacial liquid-liquid ion transport is of crucial importance to biotechnology and industrial separation processes including nuclear elements and rare earths. A water-in-oil microemulsion is formulated here with density and dimensions amenable to atomistic molecular dynamics simulation, facilitating convergent theoretical and experimental approaches to elucidate interfacial ion transport mechanisms. Lutetium(III) cations are transported from the 5 nm diameter water pools into the surrounding oil using an extractant (a lipophilic ligand). Changes in ion coordination sphere and interactions between the interfacial components are studied using a combination of synchrotron X-ray scattering, spectroscopy, and atomistic molecular dynamics simulations. Contrary to existing hypotheses, our model system shows no evidence of interfacial extractant monolayers, but rather ions are exchanged through water channels that penetrate the surfactant monolayer and connect to the oil-based extractant. Our results highlight the dynamic nature of the oil-water interface and show that lipophilic ion shuttles need not form flat monolayer structures to facilitate ion transport across the liquid-liquid interface.