An in depth understanding of the atomistic mechanism underlying different electrochemical processes requires recording large sets of data under operando conditions yielding key information of the electrified interface. Thus, the desired parameters to be known include the chemical composition at the interface, chemical states of the atoms and their variation as a result of the electrochemical reactions as well as the structural evolution. Unfortunately, the analytical techniques able to provide interface information are very limited and hardly compatible with liquids allowing usually only ex situ characterizations leading to a loss of important information as in many cases the intermediates and electrocatalytic actives species cannot be “quenched” in post process analysis. X-ray spectroscopy techniques are able to provide relevant information of the electronic structure in an element specific manner but real electrochemical interfaces are buried and most of the time in presence of liquid electrolytes being inaccessible directly to the common surface sensitive techniques like photoelectron spectroscopy requiring new experimental strategies for their operation under these conditions. In this talk I will present some of the new approaches which allow the investigation of the electronic structure variation of the electrocatalysts under reaction conditions using photoelectron spectroscopy and electron spectroscopy. The operation of these approaches will be exemplified on the CO₂RR on copper electrodes. Finally, the opportunities for the characterization of electrochemical interfaces that new 3Sbar beamline offers will be introduced. The 3Sbar beamline is dedicated to surface electron spectroscopy and surface diffraction under relevant partial pressure, 1bar and beyond. This beamline is currently under construction in ALBA synchrotron.