From Lascaux to Van Gogh: From the sample analyses to non-invasive chemical imaging of paintings The analysis of works of art and archaeological objects aims at determining their exact nature, the provenance and circulation of raw materials, the transformation and manufacturing processes as well as their function und utility. Age determination and the discrimination of fakes are other important issues. They all intent to contribute to a better understanding of socio-economical organisation and the cognitive capabilities of former societies. From a physico-chemical point of view, the analyses have generally been performed on representative samples that allow the determination of trace elements, minor phases or crystal morphologies that are indicative of a special material feature or process and allow the establishment of objective criteria for answering the archaeological or arthistorical questions. Today a new trend goes towards the increasing usage of chemical imaging methods that provide the advantage of being versatile, sensitive to trace amounts of matter, non-invasive (meaning no sampling is necessary) or at least nondestructive (meaning that the sample taken is kept after the analysis). These analytical methods have been primarily used at synchrotron sources because of the brillant light they produce. These experiments inspired the development of laboratory or even portable equipment providing capabilities powerful enough to study art and archaeological objects. Through some case studies the new approaches in this interdisciplinary field of investigation are highlighted in this paper. These case studies focus mainly on the study of paint matter from Palaeolithic periods ranging to those of modern times.