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The aim of this work has been the identification of the painter's materials employed in the wall decoration of some destroyed buildings dating approximately between the first century B.C. and the first century A.D. This research originates from a previously started joined archaeological and analytical investigation concerning a varied group of findings that resulted from a rescue excavation performed by Soprintendenza Archeologica in the area of Monte d'Oro in Rome. The focus of this study progression has been directed to a numerous selection of monochrome red, pink and yellow-pigmented fragments. The analyses were performed by means of scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDX) combined with Raman and Fourier transform infrared (FTIR) spectroscopies; visible reflectance measurements have also been carried out and the relevance of this technique in such a kind of archaeological studies has been highlighted. Most attention has been given to the assessment of the performances of non-destructive techniques achieved by portable Raman, and visible reflectance instrumentation to test their diagnostic capabilities. In addition to the expected and well-known pigments such as cinnabar, red ochre, hematite for the reds and yellow ochre for the yellows, the study highlighted a diffuse use of mixed colours and in some cases the possible presence of overlapped painted layers and confirmed the presence of gildings. Among the mixtures of pigments, the most singular outcome concerns the pink fragments revealing the possible application of bone white, which seems to be rather uncommon as a pigment in Roman wall decorations. [ABSTRACT FROM AUTHOR]