Remains of pictorial decorations in a series of six representative megalithic monuments of Brittany (France) and two French stelae have been studied by micro-Raman spectroscopy for the first time. Fungal colonies on the painted orthostats made it difficult to obtain in situ Raman spectra of the paint components. Nevertheless, paint micro-specimens studied in the laboratory by micro-Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electronic microscopy combined with energy dispersive X-ray spectroscopy have made possible to characterise the materials present. The minerals α-quartz, albite, microcline, muscovite, phlogopite, celadonite, beryl and anatase have been identified in the granitic rocks supporting the paintings, while dolomite and calcite are dominant in the calcareous rocky substrata. Haematite is the main component of the red pictographs, whereas amorphous carbon and manganese oxides/oxihydroxides have been used in the black ones. Calcite, gypsum and amorphous carbon have been detected as additional components of the paint in some cases. Contamination with modern tracing materials (polystyrene and ε-copper-phthalocyanine blue) has been detected in several cases. The presence of pigments as decorative elements in megalithic monuments of Western France and its possible relation with those of the Iberian Peninsula create interesting expectations for the knowledge of the European megalithic culture.