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In this paper, we report a few examples showing how energy dispersive XRF analysis (EDXRF) coupled with visible reflectance spectroscopy (vis‐RS) can be successfully applied for the investigation of wood or canvas paintings by performing stratigraphic analyses with non‐invasive techniques. The specific aim is to reconstruct layers and their thicknesses. The method has been tested in the laboratory on paint layers similar to traditional Renaissance ones. In situ analyses of a famous wood painting by Andrea Mantegna—‘Madonna col bambino e un coro di cherubini’, Pinacoteca di Brera, Milan—were also carried out. While illustrating the results concerning the identification of pigments and the discrimination of layer stratigraphy, advantages and limitation of this method are pointed out. Copyright © 2007 John Wiley & Sons, Ltd.

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In the field of cultural heritage analyses, energy dispersive X-ray fluorescence is a well known nondestructive technique used -among other applications -to characterize pigments and inks in artifacts such as paintings, polychromous sculptures and illuminated manuscripts. In this paper, we report on the performance of three portable X-ray fluorescence analyzers currently used for laboratory or in situ analyses. The three spectrometers have been tested in laboratory on paint layers prepared to simulate real ones, with the specific goal to determine advantages and disadvantages for each instrument in the detection of specific elements characterizing the pigment. Additionally, overall general advantages and limitations of each system in practical use are highlighted.