We demonstrate that the X-ray standing wave (XSW) technique is a powerful probe of the electrical double-layer (EDL) structure. Measurements were made of Sr adsorption at the rutile (110)-water interface from aqueous solutions. Our results show that Bragg XSW, using small-period standing waves generated by Bragg diffraction from the substrate, precisely probes the location of ions within the condensed layer, and the in situ partitioning of ions between the condensed and diffuse layers. Such measurements can provide important constraints for the development and verification of theoretical models that describe ion adsorption at the solid-water interface.