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 function-alities derived from their spatial organization. Here, CuO and Fe 2 O 3 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 satu-rated it and crystallized at the surface, forming a hierarchical microstructure. The surface microstructure consisted of crystal-lizations of Tenorite (CuO) forming interconnected walls. The walls surrounding areas of glassy matrix gave rise to a cells microstructure. Rutherford Backscattering Spectrometry pro-vided the composition of the samples with high depth resolu-tion, 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 hier-archical surface microstructure.