Relative chronology of Palaeolithic drawings of the Great Ceiling, Rouffignac cave, by chemical, stylistic and superimposition studies

•Rouffignac Cave is a UNESCO World Heritage rock-art site.•The cave plays a significant role in the prehistoric landscape in Dordogne, France.•Systematic in-situ non-invasive chemical study by portable X-ray fluorescence.•It constitutes the most extensive chemical analysis of cave art to date.•Research combines chemical, stylistic and superimposition studies.•This approach provides a new understanding of the organization of the rock art.•Three different crayon types were used on the Great Ceiling.•The subsets of figures are likely made by an artist group in a short period of time.