Synchrotron X-ray reflectivity is used to study ion distributions at the liquid-liquid interface between a nitrobenzene solution of tetrabutylammonium tetraphenylborate (TBATPB) and a water solution of tetrabutylammonium bromide (TBABr). The concentration of TBABr is varied to alter the ion distribution. Our X-ray measurements are inconsistent with several commonly used theories of ion distributions, including Gouy-Chapman, modified Verwey-Niessen, and the MPB5 version of the Poisson-Boltzmann equation. These structural measurements are described well by ion distributions predicted by a version of the Poisson-Boltzmann equation that explicitly includes a free energy profile for ion transfer across the interface when this profile is described by a simple analytic form or by a potential of mean force from molecular dynamics simulations. These X-ray measurements from the liquid-liquid interface provide evidence for the importance of interfacial liquid structure in determining interfacial ion distributions. (c) 2006 Elsevier B.V. All rights reserved.