This paper presents the first systematic chemical study of the black pigments used on the Great Ceiling panel at Rouffignac Cave in combination with stylistic and superimposition studies. A refined quantification strategy was designed to address the large number of drawings and the considerable amount of data required for the effective study of the specific black compositions on the Great Ceiling. We show that at least three different types of barium-bearing manganese oxides (that could be assimilated to different black raw coloring materials) were used. The new chemical data obtained are interpreted in light of stylistic and superimposition analyses of the figures. The grouping of the figures in small subsets according to chemical composition and consideration of superimpositions allowed for a complete re-reading of this complex panel and suggests that a small group of artists, each using different crayons, may have drawn the figures in a short period of time.