X-Ray standing wave (XSW) measurements were made of Rb and Sr adsorbed from aqueous solutions at the rutile (110)-water interface. These experiments were performed to address the extent to which direct measurements of electrical double-layer structure are possible. The experimental results show that the Bragg XSW technique, using small-period standing waves generated by Bragg diffraction from the substrate, can precisely measure ion locations within the condensed layer and the in situ partitioning of ions between the condensed and diffuse layers. Differences in condensed layer ion positions were observed for Sr ions (measured in situ) as compared with Rb ions (in situ) and also for Sr ions (ex situ). An additional constraint on the ex situ Sr site geometry was provided by polarization-dependent surface EXAFS measurements. Such measurements can provide important constraints for the development and verification of electrical double-layer theory especially as applied to ion adsorption at the solid-water interface.