X-Ray Diffraction in grazing incidence is a well-established technique to probe surfaces at the atomic level. Structural information can be extracted only for well-prepared surfaces, usually in ultra-high vacuum environment (UHV). The same technique can be applied to the interface between a solid substrate and a liquid, e.g. water bonding on a surface or interaction with a liquid electrolyte, and gives access to informations such as surface coverage and roughness in order to build up a 3D image of the electrode surface at the atomic scale. Several examples will be shown to illustrate such experiments performed on ID32 beamline using a portable chamber to maintain the UHV conditions during measurement after preparation in a UHV lab and allowing the subsequent contact with the electrochemical cell in controlled atmosphere.