AbstractThe aim of this study is to investigate the yellow pigments based on lead, tin, and antimony produced according to the ancient treatises, recipe books, and literary sources. The pigments considered in this study are lead/tin yellow type I (Pb2SnO4), lead/tin yellow type II (PbSn1−xSixO3), lead antimonate or Naples yellow (Pb2Sb2O7), and lead/tin/antimony yellow (Pb2SnSbO6,5). Color was measured by X‐Rite reflectance spectrophotometer to investigate the chromatic characteristics of the produced pigments in relation to the recipes. The pigments were chemically characterized by scanning electron microscopy with energy‐dispersive spectroscopy, and micro‐Raman analysis to investigate the influence of reagents, temperature, and melting modalities in the compositions of the produced powders. A part of the study was devoted to the study on the use of these yellow pigments in the art history especially concerning the modus pingendi of Italian artists between 14th and 18th century. The results of this study highlighted the possibility to obtain pigments with different colors and compositions according to the reagents, to the temperature, to the melting modality, in particular if single or double firing was used. © 2016 Wiley Periodicals, Inc. Col Res Appl, 41, 226–231, 2016