We have used synchrotron-based X-ray fluorescence imaging (XRFI) to examine sherds of painted ceramics from prehistoric cultures of the American Southwest. These sherds are very well suited to XRFI analysis. Paints can generally be detected and distinguished by the fluorescence intensities of their constituent elements. Spatial maps of element distributions yield the spatial distribution of pigments. Pigments can be distinguished that are (or have become) visually similar; layers that have been obscured by overpainting can be examined; and pigment residues can be distinguished from surface contaminants deposited after painting and firing. As a result, XRFI allows the painted motifs to be clarified and hidden features to be revealed. Furthermore, the very rapid scanning and high sensitivity elemental detection possible with synchrotron-based XRFI facilitate measurements on large collections of sherds, allowing an integrative rather than anecdotal analysis. © 2013 Elsevier Ltd.