The electrode/electrolyte interface is central to many electrochemical systems; however, gaining insight into the electronic structure at the interface is challenging. Due to its buried nature it is difficult to employ traditional techniques that provide spectroscopic information of localised atoms. To gain new insight into the charge distribution at the interface, we used resonant surface X-ray diffraction to select atoms at the interface via the diffraction conditions and obtained spectroscopic information simultaneously. Coupling the polarisation of the incident X-ray beam with the electron density at the interface allows direct probing of the charge transfer between the metal electrode and the adsorbing species in the electrolyte solution. Results for the adsorption of halide anions onto Cu and Au single crystal electrode surfaces reveal that there is significant modification of the charge distribution of both the surface and sub-surface atomic metal adlayers in the case of ionic bond formation. This has potential impact both in developing a theoretical understanding of the interface structure and in designing new materials for electrochemical applications.