No / The adoption of mineral pigments for artistic expression can be traced back to the paintings of the Magdalenian and Cro-Magnon cultures of about 25 000 years BCE, wherein a limited range of oxides such as pyrolusite, goethite, and hematite were utilized along with the first synthetic pigment, carbon, to decorate cave dwellings with surprisingly lifelike images. The growth of chemistry created a new palette of colors, culminating in the preparation of organic dyes and pigments in the mid-nineteenth century. The historical usage of mineral pigments largely based on metal sulfides, oxides, carbonates, sulfates, and nitrates followed by early natural organic extracts from botanical and insect species such as dragon's blood, indigo, gamboge, and cochineal that were later partially superseded by a wide range of synthetic azo dyes is described, where possible alongside their accepted date of first adoption in artworks; while this is relatively easy to define in the case of synthetic materials, it is rather more conjectural for the establishment of an historical timeline for naturally occurring minerals. The characterization of pigments using analytical chemical techniques applied to artworks and artifacts can therefore be used to identify an out-of-context material in an otherwise perfectly acceptable work of art sufficient to render an appellation of ‘fake’ being applied to the object. However, unrecorded later restoration whereby an artwork has been retouched using modern, more stable pigments replacing their more fugitive analogues can cause problems in this respect. In this article, the mineral pigments used are tabulated along with their synthetic counterparts that frequently have precise dates for their appearance in the chemical literature giving rise to a contextual and chronological aspect to analytical science applied to artworks – a forensic art theme. Much work has recently been discussed in the analytical discrimination between natural mineral pigments used historically and their more recent synthetic counterparts: here, terminological differences are critically important and often lacking – hence, the confused usage of terms such as cinnabar and vermilion, lapis lazuli and ultramarine, which are to be found in artists' manuals and contemporary texts.