This paper offers a broad and critical overview of current discussions on the potential uses and the characterization of pigments in prehistory, with a special focus on prehistoric rock art. Today, analytical approaches to pigments and paints allow us to go beyond the identification of the elemental and molecular composition of these archaeological remains, to explore also raw material procurement, transformation and use strategies of interest to investigate the technological and socio-cultural practices of prehistoric artists and their change over space and time. The paper also summarizes the palette of prehistoric artists, as well as the techniques and analytical strategies used to date to characterize prehistoric pigments and paints (colours, raw materials, binders and recipes) used in prehistoric rock art.