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Is it possible to detect rock paintings coated by natural or anthropic concretions? In this work, a methodology to discover and characterize underlying paintings is proposed. This approach combines chemical studies by micro-Raman and SEM-EDS of micro-stratigraphic samples taken from the paintings and support rock. As a case of study, it is described the research performed in the archeological site of Oyola in the northwest of Argentina. Strong evidences of red, black, and white hidden paintings have been found. In addition, the method herein presented is thoroughly evaluated pointing out their possibilities and limitations as a tool for the understanding of the historical processes involving production and transformation of the rock art panels. To this end, the methodology was proofed to be a successful exploratory approach for painting detection, expanding its capabilities when complemented with non-invasive characterization techniques.