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Copper and iron in glasses constitute classical aims of study because of the optical effects that they produce. Structured materials are also interesting due to the incorporated functionalities derived from their spatial organization. Here, CuO and Fe2O3 were incorporated into a standard glass, from which glass coatings with different thicknesses were studied. Whereas iron cations dissolved in the glassy matrix, copper cations saturated it and crystallized at the surface, forming a hierarchical microstructure. The surface microstructure consisted of crystallizations of Tenorite (CuO) forming interconnected walls. The walls surrounding areas of glassy matrix gave rise to a cells microstructure. Rutherford Backscattering Spectrometry provided the composition of the samples with high depth resolution, and Raman Confocal Microscopy determined the phases location and their distribution forming the microstructure. The joint information from both techniques allowed high chemical and spatial resolution of the main cations location for the hierarchical surface microstructure.