Spanning from nanoelectronics to new solar energy materials, technological development in the recent years requested highly controlled nanostructured surfaces, ultra-thin films, and 2D structured materials. In general, although very favorable from a full life cycle assessment (FLCA) standpoint, electrodeposition hardly allows to obtain the high order required by recent technologies. In particular cases, the electrodeposition enables the deposition of atomic layers by means of surface limited reactions (SLRs). By exploiting SLRs, it is possible to define layer-by-layer deposition scheme of different atomic layers; we refer to these schemes as electrochemical atomic layer deposition (E-ALD) and when the growth of the film is epitaxial with the substrate, the techniques are called electrochemical atomic layer epitaxy (ECALE). Aiming at characterizing structure and growth of materials grown by means of E-ALD, surface analysis techniques apply better. In particular, surface X-ray diffraction (SXRD) with high brilliance synchrotron sources enables the operando structural analysis in electrochemical environment. In recent years, several works on the operando surface characterization by means of SXRD have been reported. Thanks to novelties in the field of operando SXRD experiments, semiconducting systems were studied, such as single and multilayer of CdS and Cu2S.