Abstract Lead‐rich blue‐and‐white tile glazes (16th to 17th century, Portuguese manufacture) were studied by x‐ray absorption near‐edge spectroscopy (XANES) to assess the speciation and coordination environment of zinc, a fuser metal commonly used along with lead in ancient glazes. Zincite (ZnO) and smithsonite (ZnCO 3 ) were used as model compounds for Zn 2+ ions in tetrahedral and octahedral coordinations, respectively and theoretical simulations of Zn 1 s XANES spectra were undertaken using the FEFF code based on the full multiple‐scattering approach. Comparison between calculated and actual spectra collected from the glazes showed differences that are discussed in terms of oxygen‐anion linkages within the silica‐rich glassy matrix. Obtained results support the conclusion that zinc assumes a low‐coordination environment, most probably tetrahedral, in the studied ancient tile glazes. Copyright © 2008 John Wiley & Sons, Ltd.