The first purpose of this paper is to underline a relevant colorimetric co-ordinate characterizing the colour of ochres within their extremely wide range, from pale yellow to dark red. The second purpose is to link together quantitatively the variations of this colorimetric co-ordinate and the various chemical compositions of the samples, mainly hematite, goethite and white pigments. A group of 30 modern ochres and a group of 20 ancient ochres have been investigated. All these natural pigments have been commercialized. Diffuse reflectance spectrometry allows to calculate the colorimetric co-ordinates in the CIE-L*a*b* space and the position of the absorption band of each sample. Physico-chemical analysis has been obtained by quantitative X-ray diffraction, scanning and transmitting electronic microscopy and particle-size analysis by laser diffraction. The positive a* co-ordinate (redness) has been underlined, for the first time, to be the only relevant colorimetric parameter to characterize the colour of the ochres. Its variations are quantitatively connected to the shift of the absorption band due to the charge transfer between the ligand (OH− or O2−) and the Fe3+ ion contained in goethite and/or hematite. For ochres containing both hematite and goethite, the a* co-ordinate linearly increases with the relative amount of hematite while the absorption band progressively shifts towards the high wavelengths. Such a linear shift of the absorption band has never been underlined before. For ochres containing only one iron oxide, a* linearly decreases with the amount of white pigments, whatever the nature of the white charges. Moreover, this study gives the opportunity to show that only the nature, the amount and the size distribution of the white charges allow to discriminate the ochres according to their geographic origin.