AbstractThis article describes a preliminary method for pigment identification in paintings, based on the images obtained using digital microscopy with visible and infrared illumination and X‐ray fluorescence spectrometry (XRF). About 240 standards of pigments were characterized using image processing and XRF analysis, building a specific database of reference images and spectra. The advantage of this method is that mixture of pigments could be discriminated and identified. An example of the application of this data analysis of pigments in fresco paintings is presented. © 2016 Wiley Periodicals, Inc. Col Res Appl, 41, 321–324, 2016