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Being one of the ten alpine sites of schematic rock art painting, the Rocher du Château(Castle Rock) is a remarkable site situate on a main transalpine route at 1750 m.a.s.l. in the Vallée de la Maurienne (France). Despite the first mention of the presence of rock art,few studies have been carried out on this site (Nehl, 1976). Since archaeological surveys and some archaeological excavations were realized (between 1989 and 2003) attesting a Neolithic occupation and the discovery of some coloring and colored matter from the Neolithic layers attributed to the phase 2 of the ”Square Mouthed Pottery” Italian culture (4500-4000 BCE). In order to question the chronology of the ”schematic” painting phenomena occurring in the Mediterranean area, the integrated study of the Rocher du Château involved both the rock art description and the comparison between fragments of coloring materials to the painting matters preserved in the bedrock surface. By combining non-invasive in situ methods (numerical binocular and Raman spectroscopy) and micro-sampling, the understanding of weathering process before and after painting deposit is proposed and the identification of the pigment is realized. Complementary physico-chemical analyses have been developed at several scales of observation to identify various compositions of the fragments of coloring matter and of the colored pebble fragments. Thanks to these data, discussion could be proposed to understand the potential link between the artefacts, the production of coloring matter. and the application of painting matter. The presence of an extremely unusual mineral of iron silico-phosphate raises the question of the origin and of the supply in coloring matter
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