In the present article we put forward a theoretical and methodological introduction for the study of the materiality of rock paintings through their physicochemical characterisation. We discuss the main questions posed and the most commonly used techniques in the identification of the pigments, specifically inorganic components. This work, which is the result of our recent studies of rock paintings in Chile, aims at summarising in a simple way the advantages and limitations of the techniques used to answer specific questions about the technology and the origin of paints. Finally, we open the discussion of these questions to other aspects that may be approached from a physicochemical characterisation of pigments. Additionally, we make brief references to other aspects that may be analysed by combining these results with the study of the contexts of production and consumption of paints, as well as symbolic approaches to pigments.