In this work, we report the results of the in situ application of micro‐Raman spectroscopy to the analysis of two historic painted objects: a 15th‐century illuminated manuscript and a late 16th‐century portrait miniature. Both objects were unexpectedly found to contain calomel (Hg2Cl2), intentionally used as a white pigment. Calomel was a widespread and popular medicine until it fell out of use at the end of the 19th century due to its toxicity, and a material called ‘mercury white’ is referred to in 16th‐century technical literature on painting. However, although calomel has been recognised in the past as a degradation product of cinnabar in both wall and easel paintings, its deliberate use as a pigment on cultural heritage objects has only been documented recently in white areas painted on 17th‐century South American objects. The present study describes the first ever verified use of calomel as a white pigment on European works of art, both of which predate its documented use in South America.

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<p class="Abstract">In the frame of a research project involving a private collection of artworks a panel painting representing the Nursing Madonna (<em>Madonna del latte</em>) was studied by means of scientific examination.</p><p class="Abstract">The Department of Chemistry and Industrial Chemistry (DCCI) of the University of Genoa carried out non-invasive exams, combining imaging techniques with analytical analyses.</p><p class="Abstract">Infrared reflectography (IRR), infrared false colour (IRFC), UV fluorescence (UVF), X-ray fluorescence (XRF) and reflectance spectroscopy in the visible range (vis-RS) were used to analyse the painting palette thus obtaining more information on a possible creation date of the painting.</p><p class="Abstract">Some of the most interesting results are the identification of a freehand underdrawing and the usage of lead white, cinnabar, Fe-based pigments for yellows and browns and Cu-based pigments for blue and green colours.</p>The scientific results, as well as historical researches allow the hypothesis that the <em>Madonna del latte </em>was authored in the early 16^th century by a Florentine artist, probably a scholar of Baccio della Porta.